EP2145894B1 - Salts of diorganyl phosphinic acids, method for their manufacture and their application - Google Patents

Salts of diorganyl phosphinic acids, method for their manufacture and their application Download PDF

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Publication number
EP2145894B1
EP2145894B1 EP09012794A EP09012794A EP2145894B1 EP 2145894 B1 EP2145894 B1 EP 2145894B1 EP 09012794 A EP09012794 A EP 09012794A EP 09012794 A EP09012794 A EP 09012794A EP 2145894 B1 EP2145894 B1 EP 2145894B1
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EP
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Prior art keywords
diorganylphosphinic
flame
zinc
weight
melamine
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EP09012794A
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German (de)
French (fr)
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EP2145894A2 (en
EP2145894A3 (en
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Harald Dr. Bauer
Werner Dr. Krause
Martin Dr. Sicken
Norbert Dr. Weferling
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/305—Poly(thio)phosphinic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the invention relates to diorganylphosphinic acid salts, a process for their preparation and their use.
  • the object was thus to provide diorganylphosphinic acid salts which, owing to their specific composition, have improved compatibility with the polymers.
  • a further object was to provide flame retardant compositions based on the diorganylphosphinic acid salts according to the invention, furthermore flame-retardant polymer molding compositions based on diorganylphosphinic acid salts, or flame retardant compositions, and also flame-retardant polymer moldings with improved mechanical properties.
  • diorganylphosphinic acid salts having a specific content of partially water-soluble, ionizable compounds.
  • the abovementioned compounds are therefore in each case ionizable and consist of a water-soluble fraction (for example a salt which can be dissolved out of the total content of the abovementioned compounds) and a non-water-soluble fraction (for example a salt fraction which partly remains and thus is not soluble).
  • a water-soluble fraction for example a salt which can be dissolved out of the total content of the abovementioned compounds
  • non-water-soluble fraction for example a salt fraction which partly remains and thus is not soluble
  • M is aluminum, calcium, titanium, zinc, tin or zirconium.
  • R 1 , R 2 are the same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
  • the diorganylphosphinic acid salts of the formula (I) are preferably those from the group consisting of aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanylbisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanylbismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanylbisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate and any mixtures thereof.
  • the invention also relates to a process for the preparation of
  • the free base is ammonia, melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, biuret, allantoin, acetoguanamine, benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine , Acetyleneurea, hydantoin, Malonklamidamidin, dimethylurea, 5,5-Diphenylhydantoin, N, N'-diphenylurea, ethylene-bis-5-triazone, glycine anhydride, tetramethylurea, triethanolamine, condensation products of melamine z. As melem, melam or melon or higher condensed compounds of this type.
  • the free base is an oxide, mixed metal oxide hydroxide, hydroxide, carbonate, hydroxide carbonate, bicarbonate of the desired cation.
  • the desired cations are preferably Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and / or K.
  • the salt of the desired cation is fluorides, chlorides, bromides, iodides; Hypohalites, halogenites, halogenates, iodate, perhalates, perchlorate oxides, hydroxides, peroxides, superoxides; Sulphates, hydrogen sulphates, sulphate hydrates, sulphites, peroxosulphates nitrides, phosphides nitrate, nitrate hydrates, nitrites, phosphates, peroxophosphates, phosphites, hypophosphites, pyrophosphates, carbonates, bicarbonates, hydroxide carbonates, carbonate hydrates, silicates, hexafluorosilicates, hexafluorosilicate hydrates, stannates, borates, polyborates, peroxoborates, thiocyanates, Cyanates, cyanides, chromates, chromites, mo
  • the salt of the desired cation is preferably also compounds with organic anions from the group of mono-, di-, oligo-, polycarboxylic acids, eg. Formates, acetates, acetate hydrates, trifluoroacetate hydrates, propionates, butyrates, valerates, caprylates, oleates, stearates, oxalates, tartrates, citrates, citrate hydrates, benzoates, salicylates, lactate, lactate hydrates, acrylic acid, maleic acid, succinic acid, of amino acids (glycine), of acidic hydroxo-functions (phenolates etc), para-phenolsulfonates, para-phenolsulfonate-hydrates, acetylacetonate-hydrates, tannates, dimethyldithiocarbamates, trifluoromethanesulfonate, alkylsulfonates and / or aralkylsulfonates.
  • the reactive derivatives are preferably diorganylphosphinic esters, pyroesters and / or chlorides.
  • the invention also relates to the use of diorganylphosphinic salts according to one or more of claims 1 to 5 as flame retardants or in flame retardant compositions, wherein the flame retardant composition from 50 to 99.9 wt .-% of a Diorganylphosphinklare salt after one or more of claims 1 to 5 and contains 0.1 to 50 wt .-% of at least one additive and wherein the additives from the group melamine phosphate, dimelamine phosphate, Pentamelamintriphosphat, trimelamine diphosphate, Tetrakismelamintriphosphat, Hexakismelaminpentaphosphat, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, Melampolyphosphate, melem polyphosphate, melon polyphosphate; or from the group of oligomeric esters of tris (hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine,
  • the invention also relates to the use of the diorganylphosphinic acid salts according to the invention in or for the preparation of flameproofed polymer molding compositions and flameproofed polymer moldings, films, filaments and fibers.
  • the polymers come from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the thermosetting polymers.
  • the flame-retardant polymer shaped bodies, films, threads and fibers preferably contain 1 to 50% by weight of diorganylphosphinic acid salts or inventive polymer molding composition, 1 to 99% by weight of polymer or mixtures thereof, 0 to 60% by weight. % Additives and 0 to 60% by weight of filler or reinforcing materials.
  • Protonated nitrogen bases are preferably understood to mean the protonated forms of ammonia, primary, secondary, tertiary and quaternary amines, preferably the protonated forms of melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, biuret, allantoin, Acetoguanamine, benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine, acetyleneurea, hydantoin, malonic acid amidamidine, dimethylurea, 5,5-diphenylhydantoin, N, N'-diphenylurea, ethylene-bis-5-triazone, glycine anhydride , Tetramethylurea, triethanolamine, condensation products of melamine z. As melem, melam or melon or higher
  • the total content of sulfate is 2,500 to 200 ppm and more preferably 1,000 to 300 ppm and the content of water-soluble sulfate (water-soluble content of the partially water-soluble, ionizable compound) 750 to 50 ppm.
  • the residual moisture of the diorganylphosphinic acid salts according to the invention is preferably from 0.01 to 10% by weight, the particle size from 0.1 to 1000 ⁇ m and the bulk density from 80 to 800 g / l.
  • the solubility of the diorganylphosphinic acid salts according to the invention in water and / or organic solvents is preferably between 0.001 and 10% by weight.
  • the salt of the desired cation is preferably also compounds with anions from the group of monoorganylphosphinates, such as mono- (C 1-18 -alkyl) -phosphinates, mono-C 6 -C 10 -aryl phosphonates, and mono- (C 1-10 -alkyl) -phosphinates.
  • monoorganylphosphinates such as mono- (C 1-18 -alkyl) -phosphinates, mono-C 6 -C 10 -aryl phosphonates, and mono- (C 1-10 -alkyl) -phosphinates.
  • C 1-18 aralkyl) phosphinates e.g.
  • the salt of the desired cation is salts of protonated nitrogen bases, for.
  • Example of ammonia, primary, secondary, tertiary and quaternary amines eg. Melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, allantoin, acetoguanamine, Benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine, acetyleneurea, hydantoin, malonic acid amidamidine, dimethylurea, 5,5-diphenylhydantoin, N, N'-diphenylurea, ethylene-bis-5-triazone, glycine anhydride, tetramethylurea , Triethanolamine, condensation products of melamine z. As melem, melam or melon or
  • the invention also relates to the use of the diorganylphosphinic acid salts according to the invention as flame retardants, in particular in polymers or in flame retardant compositions, in particular for polymers.
  • the flame retardant composition contains 95 to 70 wt .-% of Diorganylphosphinklare salt according to the invention and 5 to 30 wt .-% of at least one additive.
  • the mean particle size of the flame retardant composition is preferably from 0.1 to 3,000 ⁇ m, in particular from 1 to 100 ⁇ m.
  • the residual moisture of the flame retardant composition is preferably from 0.01 to 10% by weight, preferably from 0.1 to 1% by weight.
  • the invention also relates to the use of the diorganylphosphinic salts according to the invention in or for the production of flame-retardant polymer molding compositions.
  • the flame-retardant polymer molding composition contains 1 to 50 wt .-% diorganylphosphinic according to the invention salts, 1 to 99 wt .-% polymer or mixtures thereof.
  • the flame-retardant polymer molding composition preferably comprises 1 to 50% by weight of diorganylphosphinic acid salts according to the invention, 1 to 99% by weight of polymer or mixtures thereof and 0.1 to 60% by weight of additives.
  • the polymers come from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the thermosetting polymers.
  • the polymer molding composition was preferably obtained by mixing the diorganylphosphinic acid salts and / or the flame retardant compositions with the polymer granules and any additives in a mixer, homogenizing them in a compounding unit at elevated temperatures in the polymer melt and then stripping off the homogenized polymer strand , cooled and portioned.
  • Suitable compounding units are single-screw extruders, multi-zone screws or twin-screw extruders.
  • the flame-retardant polymer shaped bodies, films, threads and fibers preferably comprise 1 to 50% by weight of diorganylphosphinic acid salts according to the invention, 1 to 99% by weight of polymer or mixtures thereof, 0.1 to 60% by weight of additives and 0 , 1 to 60 wt .-% filler or reinforcing materials.
  • the flame-retardant polymer moldings, films, filaments and fibers preferably comprise from 1 to 70% by weight of flameproofing composition according to the invention or flameproofed polymer molding composition according to the invention, from 1 to 99% by weight of polymer or mixtures thereof, from 0.1 to 60% by weight. % Additives and 0.1 to 60% by weight of filler or reinforcing materials.
  • the processing temperatures at polystyrene 170 to 200 ° C, polypropylene 200 to 300 ° C, polyethylene terephthalate (PET) 250 to 290 ° C, polybutylene terephthalate (PBT) 230 to 270 ° C, polyamide 6 (PA 6) 260 to 290 ° C, Polyamide 6.6 (PA 6.6) 260 to 290 ° C, polycarbonate 280 to 320 ° C.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PA 6 polyamide 6
  • PA 6.6 Polyamide 6.6
  • a flame-retardant polymer molding compound is preferred by injection molding and pressing, foam injection molding, internal gas pressure injection molding, Blow molding, film casting, calendering, laminating, coating, etc. processed to the flame-retardant polymer molding.
  • the processing temperatures in the above-mentioned method are 200 to 250 ° C in the case of polystyrene, 200 to 300 ° C. in the case of polypropylene, 250 to 290 ° C. in the case of polyethylene terephthalate (PET), 230 to 270 ° C. in the case of polybutylene terephthalate (PBT), and 6 to polyamide 6 (PA 6) 260 to 290 ° C, in the case of polyamide 6.6 (PA 6.6) 6.6 260 to 290 ° C, in the case of polycarbonate 280 to 320 ° C.
  • the compatibility of an additive with a polymer can be expressed in terms of how much the average molecular weight is reduced in the processing of a polymer by the additive.
  • a characteristic of the untreated polymer characteristic of the average molecular weight is compared with the characteristic number of the additive-treated polymer.
  • One such dimensionless index is the specific viscosity (SV value). This is derived from the determination of the viscosity of a solution of the polymer in a solvent. The viscosity of the polymer solution is set in relation to the viscosity of the pure solvent.
  • the compatibility is expressed by the SV number. After that, the compatibility (SV number) improves z. B. with polybutylene terephthalate from a certain content of partially water-soluble ionizable compounds leaps and bounds.
  • SV numbers of from 750 to 1400 are preferred, and from 850 to 1250 are particularly preferred.
  • the SV number can be determined by a polymer molding composition according to the invention or by a polymer molding.
  • volume flow index MFI, MVR
  • MFI volume flow index
  • the value is from 2 to 200 cm 3 / min (275 ° C., 5 kg).
  • the partially water-soluble, ionizable compounds are, for. B. to substances from the group of inorganic, organic, especially organophosphorus salts and mixtures thereof.
  • Also partially water-soluble, ionizable compounds with organic anions from the group of mono-, di-, oligo-, polycarboxylic acids eg. Formates, acetates, acetate hydrates, trifluoroacetate hydrates, propionates, butyrates, valerates, caprylates, oleates, stearates, oxalates, tartrates, citrates, citrate hydrates, benzoates, salicylates, lactate, lactate hydrates, acrylic acid, maleic acid, succinic acid, of amino acids (glycine), of acidic hydroxy functions (phenates etc.), para-phenol sulfonates, para-phenolsulfonate hydrates, acetylacetonate hydrates, tannates, dimethyldithiocarbamates, trifluoromethanesulfonate, alkylsulfonates, aralkylsulfonates.
  • Formates acetates
  • Monoorganylphosphinate such as mono- (C 1-18 alkyl) -phosphinates, mono- (C 6 -C 10 aryl) -phosphinates, mono- are preferred (C: 1 - 18 -Aralkyl) phosphinates z.
  • monomethylphosphinates Monoethylphosphinate, Monobutylphosphinate, Monohexylphosphinate, Monophenylphosphinate, Monobenzylphosphinate etc.
  • Monoorganylphosphonate such as mono- (C 1 - 18 alkyl) phosphonates, mono-C 6 -C 10 aryl) phosphonates, mono - (C 1 - 18 aralkyl) phosphonates z.
  • Monomethylphosphonate Monoethylphosphonate, Monobutylphosphonate, Monohexylphosphonate, Monophenylphosphonate, Monobenzylphosphonate etc.
  • any mixtures can be used according to the invention. Preference is given to partially water-soluble, ionizable compounds with cations of the alkali metals and with cations of protonated nitrogen bases z. Example of ammonia, primary, secondary, tertiary and quaternary amines.
  • Sources can z. B. be the solvent and / or the starting compounds.
  • the content of partially ionizable compounds is to be considered differentiated.
  • the total content present in the metal diorganophosphinate (total content) is important. Total contents of from 8,200 to 100 ppm, more preferably 7,000 to 200 ppm, are preferred.
  • a particle size above the preferred range makes the uniform distribution of the diorganylphosphinic acid salts according to the invention more difficult, a particle size below the preferred range makes incorporation more difficult because of increased dust formation and the risk of explosion. Residual moistures above the inventively preferred ranges cause increased polymer degradation.
  • Aluminiumtrisdiethylphosphinat invention undergoes at 160 to 200, preferably 175 to 185 ° C, a reversible crystal transformation (from X-ray powder data). Such conversion may be advantageous in processing with plastics.
  • the diorganylphosphinic acid salts according to the invention have a preferred content of initiator end groups of from 0.0001 to 10 mol%, particularly preferably from 0.001 to 1 mol%. Initiator end groups may remain attached to the last molecule of the radical chain during radical chain termination upon addition of the olefin to the hypophosphite.
  • the diorganylphosphinic acid salts according to the invention have preferred L color values of 85 to 99.9, more preferably 90 to 98.
  • the diorganylphosphinic acid salts of the invention have preferred a color values of from -4 to +9, more preferably from -2 to +6.
  • the diorganylphosphinic acid salts of the invention have preferred b color values of from -2 to +6, more preferably from -1 to +3.
  • the color values are specified in the Hunter system (CIE-LAB system, Commission Internationale d'Eclairage).
  • Diorganylphosphinic acid salts with L values below or with a or b values outside the range according to the invention require a higher use of white pigment. This deteriorates the mechanical stability properties of the polymer molding (eg modulus of elasticity).
  • the diorganylphosphinic acid salts according to the invention show improved compatibility with a variety of polymers which are used in flameproofed polymer molding compositions according to the invention or flameproofed polymer moldings according to the invention, e.g. As in polyolefins, polystyrenes and polystyrene copolymers, polyacrylates and polymethacrylates, vinyl and allyl polymers, homo- and co-polymers of unsaturated alcohols, polyacetals, polyphenylene sulfides, polyamides and co-polyamides, polyesters, polycarbonates.
  • polyolefins polystyrenes and polystyrene copolymers
  • polyacrylates and polymethacrylates vinyl and allyl polymers
  • homo- and co-polymers of unsaturated alcohols polyacetals
  • polyphenylene sulfides polyamides and co-polyamides
  • polyesters polycarbonates.
  • the diorganylphosphinic acid salt is prepared by reacting the diorganylphosphinic acid with elemental metal, or a metal salt for 0.01 to 1 hours at 0 to 300 ° C.
  • Preferred metal salts are metal oxides, mixed metal oxide hydroxides, hydroxides, etc.
  • the diorganylphosphinic acid salt is prepared by reacting the diorganylphosphinic acid with a free base at 0 to 300 ° C for 0.01 to 1 hours.
  • the diorganylphosphinic acid salt of the invention is prepared by reacting the diorganylphosphinic acid in the form of an alkali metal salt with a salt of the desired cation at 0 to 300 ° C for from 0.01 to 1 hour.
  • Preferred salts which provide the desired cations are acetates, hydroxoacetates, chlorides, hydroxochlorides, nitrates, sulfates, hydroxosulfates.
  • Their concentration in the aqueous solution is preferably from 5 to 95% by weight (anhydrous solid), more preferably from 20 to 50% by weight.
  • Alkali metal diorganophosphinic acid salts are preferred in anhydrous, hydrated or dissolved form. These alkali metal Diorganylphosphinklare salts according to the invention have a preferred solubility in water and / or the usual organic solvents between 1 and 70 wt .-% (anhydrous solid).
  • the diorganylphosphinic acid salts of the desired cation according to the invention have a preferred solubility in water and / or the customary organic solvents of between 0.001 and 10% by weight (anhydrous solid).
  • the diorganylphosphinic acid salt of the invention is prepared by reacting a diorganylphosphinic acid in the form of a reactive derivative with a derivative of the desired cation for 0.01 to 1 hour at 0 to 300 ° C.
  • Preferred diorganylphosphinic acid derivatives are diorganylphosphinic acid esters, pyroesters, chlorides, phosphates, acetates, phenolates, etc.
  • the invention also relates to the use of the diorganylphosphinic acid salts of the invention as flame retardants and in flame retardant compositions. For this purpose, they are preferably used together with other additives.
  • the flame retardant composition according to the invention particularly preferably contains 95 to 70% by weight of a diorganylphosphinic acid salt according to the invention and 5 to 30% of at least one additive
  • Preferred further additives in flame retardant compositions are e.g. B. synergists as in DE-A-2827867 . DE-A-19933901 . DE-A-19614424 . DE-A-19734437 described.
  • melamine phosphate for. Example Melapur ® MP of Messrs. Ciba-DSM Melapur
  • dimelamine phosphate Pentamelamintriphosphat, Trimelamindiphosphat, Tetrakismelamintriphosphat, Hexakismelaminpentaphosphat, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphates, Melampolyphosphate, Melempolyphosphate and / or melon polyphosphates or mixtures thereof prefers.
  • condensation products of melamine eg melam, melem and / or melon
  • reaction products of melamine with phosphoric acid e.g. melam, melem and / or melon
  • reaction products of condensation products of melamine with phosphoric acid and mixtures of the said products are preferred ( WO-96/16948 ).
  • the reaction products with phosphoric acid are compounds which are formed by reacting melamine or the condensed melamine compounds such as melam, melem or melon, etc., with phosphoric acid. Examples of these are melamine polyphosphate, melampolyphosphate and melem polyphosphate or mixed polysalts ( WO-98/39306 . WO-98/45364 . WO-98/08898 ).
  • synergists are oligomeric esters of tris (hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine condensation products such as melam, melem and / or melon, melamine cyanurate, dicyandiamide and / or guanidine.
  • Nitrogen-containing phosphates of the formulas (NH 4 ) yH 3 -yPO 4 or (NH 4 PO 3 ) z, where y is 1 to 3 and z is 1 to 10 000, are furthermore preferred according to the invention as synergists.
  • Preferred further additives in flame retardant compositions are according to EP-A-1024167 Oxygen compounds of silicon, magnesium compounds, metal carbonates of metals of the second main group of the periodic table, red phosphorus, zinc or aluminum compounds.
  • Preferred further additives in flame retardant compositions are oxides, hydroxides, carbonates, silicates, borates, stannates, mixed oxide hydroxides, oxide-hydroxide-carbonates, hydroxide-silicates or hydroxide-borates or mixtures thereof.
  • Preferred further additives in flame retardant compositions are magnesium oxide, magnesium hydroxide, hydrotalcites, dihydrotalcite, magnesium carbonates or magnesium calcium carbonates; Calcium hydroxide, calcium oxide and hydrocalumite; Zinc oxide, zinc hydroxide, tin oxide hydrate, zinc carbonate, stannate, hydroxystannate, basic zinc silicate, phosphate, borate, molybdate or sulfides; Alumina, aluminum hydroxide, boehmite, gibbsite or aluminum phosphate, manganese oxide, manganese hydroxide, tin oxide; Carbodiimides and / or (poly) isocyanates.
  • Preferred further additives in flame retardant compositions are carbonylbiscaprolactam or styrene-acrylic polymers; hindered phenols, hindered amines and light stabilizers, phosphonites, antioxidants and release agents.
  • the diorganylphosphinic acid salt according to the invention is preferably used in ready-to-use form (coated, reduced in dust, melt-granulated and / or drop-granulated, compacted, spray-granulated, dispersed, paste form and the like) in flame retardant formulations.
  • the average particle size of the flame retardant compositions of the invention is 0.1 to 3000 microns.
  • a particle size above the preferred range makes the uniform distribution of the diorganylphosphinic acid salt according to the invention more difficult
  • a particle size below the preferred range makes incorporation more difficult because of increased dust formation and the risk of explosion.
  • the preferred bulk density of the flame retardant composition of the invention is 80 to 1500 g / l, more preferably 200 to 1000 g / l; in another embodiment 80 to 800 g / l, more preferably 200 to 700 g / l and another embodiment 200 to 1500 g / l, preferably 300 to 1000 g / l.
  • the invention relates to the use of the diorganylphosphinic acid salts according to the invention and / or the flame retardant compositions in flame-retardant polymer molding compositions containing polymer.
  • preferred polymers are thermoplastic such.
  • the flame-retardant polymer molding composition 1 to 50 wt .-% diorganylphosphinic according to the invention salts or inventive flame retardant composition 1 to 99 wt .-% polymer or mixtures thereof 0 to 60 wt. -% additives.
  • the flame-retardant polymer molding composition particularly preferably contains from 5 to 30% by weight of diorganylphosphinic acid salts according to the invention or flame retardant composition according to the invention, 5 to 90% by weight of polymer or mixtures thereof 5 to 40% by weight of additives 5 to 40 wt .-% filler or reinforcing materials.
  • the polymers are preferably polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and also polymers of cycloolefins; also polyethylene (which may optionally be crosslinked) and mixtures thereof.
  • the polymers are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as.
  • ethylene-propylene copolymers mixtures of such copolymers with each other, for.
  • Copolymers and their blends with other polymers such.
  • the polymers are preferably hydrocarbon resins (eg C 5 -C 9 ) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.
  • the polymers are preferably polystyrene, poly (p-methylstyrene), poly (alpha-methylstyrene).
  • the polymers are copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength of styrene copolymers and another polymer, such as.
  • styrene such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
  • the polymers are graft copolymers of styrene or alpha-methylstyrene, such as.
  • styrene on polybutadiene and mixtures thereof, such as. B. as so-called ABS, MBS, ASA or AES polymers are known.
  • the polymers are halogen-containing polymers, such as. Polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogenated vinyl compounds, such as Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
  • halogen-containing polymers such as. Polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or
  • the polymers are preferably polymers which are derived from alpha-, beta-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, and copolymers of said monomers with one another or with other unsaturated monomers, such as. For example, acrylonitrile-butadiene copolymers.
  • the polymers are preferably polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins.
  • the polymers are preferably homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • the polymers are preferably polyacetals, such as polyoxymethylene, as well as those polyoxymethylenes, the comonomers, such as.
  • polyacetals such as polyoxymethylene
  • the comonomers such as.
  • ethylene oxide Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • the polymers are preferably polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.
  • the polymers are preferably polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof.
  • the polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2,12, polyamide 4, polyamide 4,6, polyamide 6, polyamide 6,6 , Polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6,66, polyamide 7, polyamide 7,7, polyamide 8, polyamide 8,8, polyamide 9, polyamide 9,9, polyamide 10, polyamide 10 , 9, polyamide 10, 10, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for.
  • the polymers are preferably polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
  • the polymers are preferably polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates and also block polyether esters which differ from Derive hydroxyl-terminated polyethers; also with polycarbonates or MBS modified polyester.
  • polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates and also block polyether esters which differ from Derive hydroxyl-terminated polyethers; also with polycarbonates or MBS modified polyester.
  • Suitable polymers include polycarbonates and polyestercarbonates, polysulfones, polyethersulfones and polyetherketones; crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins. Drying and non-drying alkyd resins.
  • the polymers are preferably unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their halogen-containing, hardly combustible modifications.
  • the polymers are crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.
  • the polymers are preferably alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
  • the polymers are crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. B. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, by conventional hardeners such. As anhydrides or amines can be crosslinked with or without accelerators.
  • the polymers are mixtures (polyblends) of the aforementioned polymers, such as. PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC ,
  • Preferred forms of reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer moldings are fibers, nonwovens, mats, fabrics, strands, tapes, hoses, strands, solid, molded and hollow bodies.
  • Preferred materials for reinforcing materials for flame-retardant polymer molding compounds and flame-retardant polymer molded articles are inorganic Materials such as quartz glass, carbon, minerals, metal (steel, aluminum, magnesium, molybdenum, tungsten), ceramics (metal oxides).
  • Preferred materials for reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer moldings are polycondensates such.
  • Preferred materials for reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer moldings are polymers such. Polyethylene, polypropylene, polyacrylonitrile homopolymer, polyacrylonitrile copolymer, modacrylic, atactic polyvinyl chloride, syndiotactic polyvinyl chloride, polyvinyl alcohol, polytetrafluoroethylene, polystyrene.
  • Preferred materials for reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer molded articles are natural and semisynthetic fibers (viscose cellulose, copper cellulose, cellulose acetate, cellulose triacetate, flax, hemp, sisal, jute, ramie, cotton).
  • glass fibers to polyamides within the concentration ranges of the invention results in a significant increase in strength, stiffness, softening temperature, abrasion resistance, and dimensional stability.
  • An inventive method for the production of flame-retardant polymer molding compositions is to mix the flame retardant compositions and / or Diorganylphosphinklad salts with the polymer granules and any additives in a mixer and homogenize in a compounding unit according to the invention under conditions according to the invention in the polymer melt.
  • the homogenized molding material strand is drawn off, cooled in a water bath and then granulated.
  • the flame retardant compositions and / or diorganylphosphinic acid salts and / or the additives metered in an extruder through a side feeder to the polymer stream and homogenized.
  • the flame-retardant polymer molding compositions of the invention have a residual moisture content of from 0.01 to 10% by weight, preferably from 0.1 to 1% by weight. Residual moistures above the inventively preferred ranges cause increased polymer degradation.
  • SV numbers of 750 to 1,400 are preferred, 950 to 1,300 are particularly preferred, and 1,000 to 1,200 are particularly preferred.
  • volume flow index MFI, MVR
  • MFI volume flow index
  • the value is from 2 to 200 cm 3 / min (275 ° C., 5 kg).
  • the flame-retardant polymer molding compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.
  • Preferred according to the invention is the use of the flame-retardant polymer moldings according to the invention as lamp parts such as lampholders and holders, plugs and plug strips, bobbins, housings for capacitors or contactors, as well as fuse switches, relay housings and reflectors.
  • the polymer of the shaped polymer bodies, films, filaments and fibers is preferably a thermoplastic or thermosetting polymer.
  • the modulus of elasticity of polymer moldings based on the diorganylphosphinic acid salts according to the invention, flame retardant or flameproofed molding compositions and polybutylene terephthalate, polyamide 6.6 or polyamide 6 is preferably from 10,000 to 12,000 N / mm 2 .
  • Preferred method for the production of flame-retardant polymer moldings is injection molding and pressing, foam injection molding, gas injection molding, blow molding, film casting, calendering, laminating, coating, spinning, etc.
  • Preferred additives for flame-retardant polymer molding compositions and flame-retardant polymer moldings are antioxidants, UV absorbers and light stabilizers; Lubricants, colorants, antistatic agents, nucleating agents; Fillers etc.
  • a flame retardant coating containing at least 1 to 50% of the inventive flame retardant composition is 0 to 60% ammonium polyphosphate.
  • the particle size in aqueous dispersion is determined using a granulometer Microtrac ASVR / FRA from Leeds et al. Northrup determined. The reflection or diffraction of a laser beam when penetrating the dispersion is measured. For this purpose, 400 ml of ethanol are pumped through the laser measuring cell. The solid sample (eg 70 mg) is added automatically and the particle size distribution is determined after 10 minutes. The evaluation unit of the device calculates the d50 and d90 values.
  • a sample of the diorganylphosphinic acid salt according to the invention is dissolved in a solvent (preferably water, sodium hydroxide or hydrochloric acid) and the Sulphate according to the usual methods (preferably, the ion chromatography) is quantified.
  • a solvent preferably water, sodium hydroxide or hydrochloric acid
  • 0.5 g of the polymer sample eg PBT
  • 50 ml of dichloroacetic acid (LM) into a 250 ml Erlenmeyer flask with a ground stopper.
  • the sample is dissolved with stirring at 25 ° C over a period of 16h.
  • the solution is filtered through a G1 glass frit. 20 ml of the solution are filled into the capillary into which (Ubbelohde) Capillary viscometer mounted and heated to 25 ° C.
  • dichloroacetic acid a mixture of phenol and 1,2-dichlorobenzene (1: 1, w / w) or m-cresol can also be used for polyethylene terephthalate and polybutylene terephthalate.
  • 1,2-dichlorobenzene 1,2-dichlorobenzene
  • m-cresol a mixture of phenol and 1,2-dichlorobenzene (1: 1, w / w) or m-cresol can also be used for polyethylene terephthalate and polybutylene terephthalate.
  • polyamide sulfuric acid formic acid or m-cresol can be used formic acid or m-cresol can be used.
  • the flame retardant components are mixed with the polymer granules and any additives and on a twin-screw extruder (type Leistritz LSM 30/34) at temperatures of 230 to 260 ° C (glass fiber reinforced PBT) or from 260 to 280 ° C (glass fiber reinforced PA 66) incorporated.
  • the homogenized polymer strand was stripped off, cooled in a water bath and then granulated.
  • the molding compositions were processed on an injection molding machine (Aarburg Allrounder type) at melt temperatures of 240 to 270 ° C. (glass-fiber-reinforced PBT) or from 260 to 290 ° C. (glass-fiber-reinforced PA 66) to test specimens.
  • a mixture of 50% by weight of polybutylene terephthalate, 15% by weight of phosphinic acid salt from Example 2, 5% by weight of melamine cyanurate and 30% by weight of glass fibers is added at 230 to 260 ° C. on a twin-screw extruder a polymer molding compound compounded. After drying, the molding compositions are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and an E modulus of 9,150 N / mm 2 measured.
  • a mixture of 50% by weight of polybutylene terephthalate, 15% by weight of phosphinic acid salt from Example 3, 5% by weight of melamine cyanurate and 30% by weight of glass fibers is added at 230 to 260 ° C. on a twin-screw extruder a polymer molding compound compounded. After drying, the molding compositions are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 9,573 N / mm 2 measured.
  • a mixture of 50% by weight of polybutylene terephthalate, 13.3% by weight of the phosphinic acid salt from Example 7, 6.7% by weight of melamine cyanurate and 30% by weight of glass fibers is heated on a twin-screw extruder at 230 to 260 ° C compounded to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 10,350 N / mm 2 measured. Furthermore, a UL-94 classification of V-0 was determined.
  • the composition of the flame retardant formulation comprising phosphinic acid salt and melamine cyanurate on which this example is based is based on the composition of the polymer molding composition based on polybutylene terephthalate and flame retardant formulation (containing phosphinic acid salt and melamine cyanurate) and this example lying polymer molding composition containing polymer molding composition and additives over those which give V-1 and V-2 classifications.
  • a mixture of 50% by weight of polybutylene terephthalate, 15% by weight of phosphinic acid salt from Example 8, 5% by weight of melamine cyanurate and 30% by weight of glass fibers is added at 230 to 260 ° C. on a twin-screw extruder a polymer molding compound compounded. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 10,510 N / mm 2 measured. In addition, a UL-94 classification of V-0 is determined.
  • a mixture of 50% by weight of polybutylene terephthalate, 13.3% by weight of the phosphinic acid salt from Example 7, 6.7% by weight of melamine polyphosphate and 30% by weight of glass fibers is heated on a twin-screw extruder at 230 to 260 ° C compounded to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and a UL-94 classification of V-0 determined.
  • a mixture of 50% by weight of polyamide 6.6, 13.3% by weight of phosphinic acid salt from example 2, 6.7% by weight of melamine polyphosphate and 30% by weight of glass fibers is heated to 230 on a twin-screw extruder compounded to 260 ° C to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and measured an E-modulus of 9,000 N / mm 2 . In addition, a UL-94 classification of V-0 was determined.
  • a mixture of 50% by weight of polyamide 6.6, 13.3% by weight of phosphinic acid salt from Example 8, 6.7% by weight of melamine polyphosphate and 30% by weight of glass fibers is heated to 230 on a twin-screw extruder up to 260 ° C compounded to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and an E-modulus of 11,500 N / mm 2 measured. In addition, a UL-94 classification of V-0 was determined.
  • composition of this example based flame retardant formulation containing phosphinic acid salt and melamine polyphosphate because of the more favorable UL-94 classification, the composition of this example based flame retardant formulation containing phosphinic acid salt and melamine polyphosphate, the composition of this example underlying polymer molding composition containing polyamide and flame retardant formulation (containing phosphinic acid salt and melamine polyphosphate) and the example of this underlying polymer molding composition containing polymer molding composition and additives over those giving V-1 and V-2 classifications.
  • the molding compositions are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 10,100 N / mm 2 measured.
  • a UL-94 classification of V-0 is determined.
  • a mixture of 58% by weight of polyamide 6, 11.3% by weight of phosphinic acid salt from Example 8, 5.7% by weight of melamine polyphosphate and 25% by weight of glass fibers is heated to 230 on a twin-screw extruder compounded to 260 ° C to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and a UL-94 classification of V-0 determined.
  • Saint-Gobain Glass fibers 2 PPG 3540, PPG Industries, Inc Table 1 example acetate sulfate SV index Total [ppm] Soluble [ppm] Total [ppm] Soluble [ppm] 1 (see polymer) - - - - 1386 2 (Cf.) DE19851618, Ex. 2 8800 - - - 578 3 (Cf.) DE19851618, Ex.

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Abstract

Diorganylphosphinic acid-salts and/or diorganyldiphosphinic acid-salts and/or their polymers (A) are new. Diorganylphosphinic acid-salts of formula (I) and/or diorganyldiphosphinic acid-salts of formula (II) and/or their polymers (A) are new (where the total content to the partially water-soluble, ionisable compounds and the water-soluble content of the partially water soluble, ionisable compounds amounts to about 8200 to 100 ppm (preferably 7000 to 200 ppm)). R 1>, R 2>1-6C alkyl and/or aryl; R 3>1-10C alkylene, 6-10C arylene, 6-10C alkylarylene or 6-10C arylalkylene; M : Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogenbase; and m, n, x : 1-4. Independent claims are also included for: (1) the preparation of (A); and (2) use of diorganylphosphinic acid salt (I) as flame protective agents or in flame protective composition (preferably in polymers) or for the production of flame-protective polymer molding materials, -films, -threads and -fibers.

Description

Die Erfindung betrifft Diorganylphosphinsäure-Salze, ein Verfahren zu ihrer Herstellung und ihre Verwendung.The invention relates to diorganylphosphinic acid salts, a process for their preparation and their use.

Am Stand der Technik ( US-A-3,197,436 ; US-A-3,255,125 und US-A-3,415,762 ; DE-A-196 16 025 ; DE-A-199 10 232 ; DE-A-198 51 729 ; WO-99/28327 ) ist nachteilig, dass die danach hergestellten Diorganylphosphinsäure-Salze auf Grund ihrer Zusammensetzung eine nicht ausreichende Verträglichkeit mit den Polymeren aufweisen, in denen sie eingesetzt werden sollen.In the prior art ( US-A-3,197,436 ; US-A-3,255,125 and US-A-3,415,762 ; DE-A-196 16 025 ; DE-A-199 10 232 ; DE-A-198 51 729 ; WO-99/28327 ) is disadvantageous that the diorganylphosphinic acid salts prepared thereafter due to their composition have an insufficient compatibility with the polymers in which they are to be used.

Es bestand somit die Aufgabe, Diorganylphosphinsäure-Salze bereitzustellen, die auf Grund ihrer spezifischen Zusammensetzung eine verbesserte Verträglichkeit mit den Polymeren aufweisen.The object was thus to provide diorganylphosphinic acid salts which, owing to their specific composition, have improved compatibility with the polymers.

Weiterhin bestand die Aufgabe darin Flammschutzmittel-Zusammensetzungen auf Basis der erfindungsgemäßen Diorganylphosphinsäure-Salze zur Verfügung zu stellen, weiterhin flammgeschützte Polymerformmassen basierend auf Diorganylphosphinsäure-Salzen, bzw. Flammschutzmittel-Zusammensetzungen und weiterhin flammgeschützte Polymerformkörper mit verbesserten mechanischen Eigenschaften.A further object was to provide flame retardant compositions based on the diorganylphosphinic acid salts according to the invention, furthermore flame-retardant polymer molding compositions based on diorganylphosphinic acid salts, or flame retardant compositions, and also flame-retardant polymer moldings with improved mechanical properties.

Überraschenderweise wurde nun gefunden, dass der Gehalt an teilweise wasserlöslichen, ionisierbaren Verbindungen maßgeblichen Einfluss auf die Verträglichkeit mit dem Polymer besitzt, bzw. dass ein nicht erfindungsgemäßer Gehalt an teilweise wasserlöslichen, ionisierbaren Verbindungen zu einer mangelnden Verträglichkeit von Diorganylphosphinsäure-Salzen bzw. Flammschutzmittel-Zusammensetzungen und Polymer führen kann.Surprisingly, it has now been found that the content of partially water-soluble, ionizable compounds has a significant influence on the compatibility with the polymer, or that a non-inventive content of partially water-soluble, ionizable compounds to a lack of compatibility of diorganylphosphinic salts or flame retardant compositions and polymer can lead.

Erfindungsgemäß wurde die vorgenannte Aufgabe durch Diorganylphosphinsäure-Salze mit einem spezifischen Gehalt an teilweise wasserlöslichen, ionisierbaren Verbindungen gelöst.According to the invention, the above object has been achieved by diorganylphosphinic acid salts having a specific content of partially water-soluble, ionizable compounds.

Gegenstand der Erfindung sind daher Diorganylphosphinsäure-Salze der Formel (I)

Figure imgb0001
worin

R1, R2
gleich oder verschieden sind und C1-C6-Alkyl, linear oder verzweigt und/oder Aryl;
M
Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K und/oder eine protonierte Stickstoffbase;
m
1 bis 4, und
x
1 bis 4
bedeuten, dadurch gekennzeichnet, dass der Gesamt-Gehalt an teilweise wasserlöslichen, ionisierbaren Verbindungen und der wasserlösliche Gehalt aus den teilweise wasserlöslichen, ionisierbaren Verbindungen 8.200 bis 100 ppm, und dass es sich bei den teilweise wasserlöslichen, ionisierbaren Verbindungen um solche handelt, die sich von Acetaten, Chloriden, Nitraten, Sulfaten, Phosphiten oder Phosphaten ableiten, und dass der Gesamt-Gehalt an Sulfat (teilweise wasserlösliche, ionisierbare Verbindung) 3800 bis 100 ppm, und der Gehalt an wasserlöslichem Sulfat (wasserlöslicher Gehalt aus der teilweise wasserlöslichen, ionisierbaren Verbindung) 1200 bis 10 ppm, beträgt.The invention therefore relates to diorganylphosphinic acid salts of the formula (I)
Figure imgb0001
 wherein
R 1 , R 2
are the same or different and are C 1 -C 6 -alkyl, linear or branched and / or aryl;
M
Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
m
1 to 4, and
x
1 to 4
mean, characterized in that the total content of partially water-soluble, ionizable compounds and the water-soluble content of the partially water-soluble, ionizable compounds 8.200 to 100 ppm, and that it is the partially water-soluble, ionizable compounds are those which Derived acetate, chloride, nitrates, sulfates, phosphites or phosphates, and that the total content of sulfate (partially water-soluble, ionizable compound) 3800 to 100 ppm, and the content of water-soluble sulfate (water-soluble content of the partially water-soluble, ionizable compound) 1200 to 10 ppm.

Die vorgenannten Verbindungen sind also in jedem Fall ionisierbar und bestehen aus einem wasserlöslichen Anteil (z. B. ein Salz, welches aus dem Gesamt-Gehalt der vorgenannten Verbindungen herausgelöst werden kann) und einem nichtwasserlöslichen Anteil (beispielsweise ein Salzanteil, der teilweise zurückbleibt und somit nicht löslich ist).The abovementioned compounds are therefore in each case ionizable and consist of a water-soluble fraction (for example a salt which can be dissolved out of the total content of the abovementioned compounds) and a non-water-soluble fraction (for example a salt fraction which partly remains and thus is not soluble).

Bevorzugt bedeutet M Aluminium, Calcium, Titan, Zink, Zinn oder Zirkonium.Preferably, M is aluminum, calcium, titanium, zinc, tin or zirconium.

Bevorzugt sind R1, R2 gleich oder verschieden und bedeuten Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, tert.-Butyl, n-Pentyl und/oder Phenyl.Preferably, R 1 , R 2 are the same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

Bevorzugt handelt es sich bei den Diorganylphosphinsäure-Salzen der Formel (I) um solche aus der Gruppe Aluminiumtrisdiethylphosphinat, Aluminiumtrismethylethylphosphinat, Aluminiumtrisdiphenylphosphinat, Zinkbisdiethylphosphinat, Zinkbismethylethylphosphinat, Zinkbisdiphenylphosphinat, Titanylbisdiethylphosphinat, Titantetrakisdiethylphosphinat, Titanylbismethylethylphosphinat, Titantetrakismethylethylphosphinat, Titanylbisdiphenylphosphinat, Titantetrakisdiphenylphosphinat und beliebige Mischungen davon.The diorganylphosphinic acid salts of the formula (I) are preferably those from the group consisting of aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanylbisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanylbismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanylbisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate and any mixtures thereof.

Die Erfindung betrifft auch ein Verfahren zur Herstellung vonThe invention also relates to a process for the preparation of

Diorganylphosphinsäure-Salzen der Formel (I), dadurch gekennzeichnet, dass man die Diorganylphosphinsäure

  1. a) mit einer freien Base oder
  2. b) mit dem elementarem Metall des gewünschten Kations oder
  3. c) in ihrer Form als Alkalimetall-Salz mit einem Salz des gewünschten Kations oder
  4. d) in Form eines reaktiven Derivates mit einem Derivat des gewünschten Kations 0,01 bis 1 Stunden bei 0 bis 300°C umsetzt.
Diorganylphosphinic acid salts of the formula (I), characterized in that the diorganylphosphinic acid
  1. a) with a free base or
  2. b) with the elemental metal of the desired cation or
  3. c) in its form as alkali metal salt with a salt of the desired cation or
  4. d) in the form of a reactive derivative with a derivative of the desired cation for 0.01 to 1 hours at 0 to 300 ° C.

Bevorzugt handelt es sich bei der freien Base um Ammoniak, Melamin, Harnstoff, Biuret, Guanidin, Alkylguanidin, Arylguanidin, Diphenylguanidin, Biguanid, Biuret, Allantoin, Acetoguanamin, Benzoguanamin, Tolyltriazol, Benzotriazol, 2-Amino-4-methylpyrimidin, Benzylharnstoff, Ethylendimelamin, Acetylenharnstoff, Hydantoin, Malonsäureamidamidin, Dimethylharnstoff, 5,5-Diphenylhydantoin, N,N'-Diphenylharnstoff, Ethylen-bis-5-triazon, Glycinanhydrid, Tetramethylharnstoff, Triethanolamin, Kondensationsprodukte des Melamins z. B. Melem, Melam oder Melon bzw. höher kondensierte Verbindungen dieses Typs.Preferably, the free base is ammonia, melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, biuret, allantoin, acetoguanamine, benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine , Acetyleneurea, hydantoin, Malonsäureamidamidin, dimethylurea, 5,5-Diphenylhydantoin, N, N'-diphenylurea, ethylene-bis-5-triazone, glycine anhydride, tetramethylurea, triethanolamine, condensation products of melamine z. As melem, melam or melon or higher condensed compounds of this type.

Bevorzugt handelt es sich bei der freien Base um ein Oxid, gemischtes Metall-Oxid-Hydroxid, Hydroxid, Carbonat, Hydroxidcarbonat , Hydrogencarbonat des gewünschten Kations.Preferably, the free base is an oxide, mixed metal oxide hydroxide, hydroxide, carbonate, hydroxide carbonate, bicarbonate of the desired cation.

Bevorzugt handelt es sich bei den gewünschten Kationen um Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na und/oder K.The desired cations are preferably Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and / or K.

Bevorzugt handelt es sich bei den Salz des gewünschten Kations um Fluoride, Chloride, Bromide, lodide; Hypohalogenite, Halogenite, Halogenate, lodat, Perhalogenate, PerchloratOxide, Hydroxide, Peroxide, Superoxide; Sulfate, Hydrogensulfate, Sulfathydrate, Sulfite, PeroxosulfateNitride, PhosphideNitrat, Nitrathydrate, Nitrite, Phosphate, Peroxophosphate, Phosphite, Hypophosphite, Pyrophosphate, Carbonate, Hydrogencarbonate, Hydroxidcarbonate, Carbonathydrate, Silicate, Hexafluorosilicate, Hexafluorosilicathydrate, Stannate, Borate, Polyborate, Peroxoborate, Thiocyanate, Cyanate, Cyanide, Chromate, Chromite, Molybdate, Permanganat.Preferably, the salt of the desired cation is fluorides, chlorides, bromides, iodides; Hypohalites, halogenites, halogenates, iodate, perhalates, perchlorate oxides, hydroxides, peroxides, superoxides; Sulphates, hydrogen sulphates, sulphate hydrates, sulphites, peroxosulphates nitrides, phosphides nitrate, nitrate hydrates, nitrites, phosphates, peroxophosphates, phosphites, hypophosphites, pyrophosphates, carbonates, bicarbonates, hydroxide carbonates, carbonate hydrates, silicates, hexafluorosilicates, hexafluorosilicate hydrates, stannates, borates, polyborates, peroxoborates, thiocyanates, Cyanates, cyanides, chromates, chromites, molybdate, permanganate.

Bevorzugt handelt es sich bei dem Salz des gewünschten Kations weiterhin um Verbindungen mit organischen Anionen aus der Gruppe der Mono-, Di-, Oligo-, Polycarbonsäuren, z. B. Formiate, Acetate, Acetathydrate, Trifluoracetathydrate, Propionate, Butyrate, Valerate, Caprylate, Oleate, Stearate, Oxalate, Tartrate, Citrate, Citrathydrate, Benzoate, Salicylate, Lactat, Lactathydrate, Acrylsäure, Maleinsäure, Bernsteinsäure, von Aminosäuren (Glyzin), von sauren Hydroxofunktionen (Phenolate etc), Para-Phenolsulfonate, Para-Phenolsulfonathydrate, Acetylacetonathydrate, Tannate, Dimethyldithiocarbamate, Trifluormethansulfonat, Alkylsulfonate und/oder Aralkylsulfonate.The salt of the desired cation is preferably also compounds with organic anions from the group of mono-, di-, oligo-, polycarboxylic acids, eg. Formates, acetates, acetate hydrates, trifluoroacetate hydrates, propionates, butyrates, valerates, caprylates, oleates, stearates, oxalates, tartrates, citrates, citrate hydrates, benzoates, salicylates, lactate, lactate hydrates, acrylic acid, maleic acid, succinic acid, of amino acids (glycine), of acidic hydroxo-functions (phenolates etc), para-phenolsulfonates, para-phenolsulfonate-hydrates, acetylacetonate-hydrates, tannates, dimethyldithiocarbamates, trifluoromethanesulfonate, alkylsulfonates and / or aralkylsulfonates.

Bevorzugt handelt es sich bei den reaktiven Derivaten um Diorganylphosphinsäureester, -pyroester und/oder -chloride.The reactive derivatives are preferably diorganylphosphinic esters, pyroesters and / or chlorides.

Die Erfindung betrifft auch die Verwendung von Diorganylphosphinsäure-Salzen nach einem oder mehreren der Ansprüche 1 bis 5 als Flammschutzmittel oder in Flammschutzmittel-Zusammensetzungen, wobei die Flammschutzmittel-Zusammensetzung 50 bis 99,9 Gew.-% eines Diorganylphosphinsäure-Salzes nach einem oder mehreren der Ansprüche 1 bis 5 enthält und 0,1 bis 50 Gew.-% mindestens eines Additives enthält und wobei die Additive aus der Gruppe Melaminphosphat, Dimelaminphosphat, Pentamelamintriphosphat, Trimelamindiphosphat, Tetrakismelamintriphosphat, Hexakismelaminpentaphosphat, Melamindiphosphat, Melamintetraphosphat, Melaminpyrophosphat, Melaminpolyphosphat, Melampolyphosphat, Melempolyphosphat, Melonpolyphosphat; oder aus der Gruppe oligomere Ester des Tris(hydroxyethyl)isocyanurats mit aromatischen Polycarbonsäuren, Benzoguanamin, Tris(hydroxyethyl)isocyanurat, Allantoin, Glycouril, Melamin, Melamincyanurat, Harnstoffcyanurat, Dicyandiamid, Guanidin; oder aus der Gruppe der Zinkverbindungen wie Zinkoxid, Zinkhydroxid, Zinnoxidhydrat, Zinkcarbonat, Zinkstannat, Zinkhydroxystannat, Zink-Silikat, Zinkphosphat, Zinkborat, Zinkmolybdat; oder aus der Gruppe der Carbodiimide und/oder (Poly-)isocyanate, wie Carbonylbiscaprolactam und/oder Styrol-Acryl-Polymere entstammen.The invention also relates to the use of diorganylphosphinic salts according to one or more of claims 1 to 5 as flame retardants or in flame retardant compositions, wherein the flame retardant composition from 50 to 99.9 wt .-% of a Diorganylphosphinsäure salt after one or more of claims 1 to 5 and contains 0.1 to 50 wt .-% of at least one additive and wherein the additives from the group melamine phosphate, dimelamine phosphate, Pentamelamintriphosphat, trimelamine diphosphate, Tetrakismelamintriphosphat, Hexakismelaminpentaphosphat, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, Melampolyphosphate, melem polyphosphate, melon polyphosphate; or from the group of oligomeric esters of tris (hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, guanidine; or from the group of zinc compounds such as zinc oxide, zinc hydroxide, tin oxide hydrate, zinc carbonate, zinc stannate, zinc hydroxystannate, zinc silicate, zinc phosphate, zinc borate, zinc molybdate; or from the group of carbodiimides and / or (poly) isocyanates, such as carbonylbiscaprolactam and / or styrene-acrylic polymers.

Die Erfindung betrifft auch die Verwendung der erfindungsgemäßen Diorganylphosphinsäure-Salze in oder zur Herstellung von flammgeschützten Polymerformmassen und flammgeschützten Polymerformkörpern, -Filmen, -Fäden und -Fasern.The invention also relates to the use of the diorganylphosphinic acid salts according to the invention in or for the preparation of flameproofed polymer molding compositions and flameproofed polymer moldings, films, filaments and fibers.

Bevorzugt entstammen dabei die Polymere aus der Gruppe der thermoplastischen Polymere wie Polyester, Polystyrol oder Polyamid und/oder der duroplastischen Polymere.Preferably, the polymers come from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the thermosetting polymers.

Bevorzugt enthalten bei dieser Verwendung die flammgeschützten Polymerformkörper, -Filme, -Fäden und -Fasern 1 bis 50 Gew.- % erfindungsgemäße Diorganylphosphinsäure-Salze oder erfindungsgemäße Polymerformmasse, 1 bis 99 Gew.-% Polymer oder Mischungen derselben, 0 bis 60 Gew.-% Additive und 0 bis 60 Gew.-% Füllstoff bzw. Verstärkungsmaterialien.In this use, the flame-retardant polymer shaped bodies, films, threads and fibers preferably contain 1 to 50% by weight of diorganylphosphinic acid salts or inventive polymer molding composition, 1 to 99% by weight of polymer or mixtures thereof, 0 to 60% by weight. % Additives and 0 to 60% by weight of filler or reinforcing materials.

Unter protonierten Stickstoffbasen werden bevorzugt die protonierten Formen von Ammoniak, primären, sekundären, tertiären und quartären Aminen verstanden, bevorzugt die protonierten Formen von Melamin, Harnstoff, Biuret, Guanidin, Alkylguanidin, Arylguanidin, Diphenylguanidin, Biguanid, Biuret, Allantoin, Acetoguanamin, Benzoguanamin, Tolyltriazol, Benzotriazol, 2-Amino-4-methylpyrimidin, Benzylharnstoff, Ethylendimelamin, Acetylenharnstoff, Hydantoin, Malonsäureamidamidin, Dimethylharnstoff, 5,5-Diphenylhydantoin, N,N'-Diphenylharnstoff, Ethylen-bis-5-triazon, Glycinanhydrid, Tetramethylharnstoff, Triethanolamin, Kondensationsprodukte des Melamins z. B. Melem, Melam oder Melon bzw. höher kondensierte Verbindungen dieses Typs.Protonated nitrogen bases are preferably understood to mean the protonated forms of ammonia, primary, secondary, tertiary and quaternary amines, preferably the protonated forms of melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, biuret, allantoin, Acetoguanamine, benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine, acetyleneurea, hydantoin, malonic acid amidamidine, dimethylurea, 5,5-diphenylhydantoin, N, N'-diphenylurea, ethylene-bis-5-triazone, glycine anhydride , Tetramethylurea, triethanolamine, condensation products of melamine z. As melem, melam or melon or higher condensed compounds of this type.

Bevorzugt beträgt der Gesamt-Gehalt an Sulfat (teilweise wasserlösliche, ionisierbare Verbindung) 2.500 bis 200 ppm und besonders bevorzugt 1.000 bis 300 ppm und der Gehalt an wasserlöslichem Sulfat (wasserlöslicher Gehalt aus der teilweise wasserlöslichen, ionisierbaren Verbindung) 750 bis 50 ppm.Preferably, the total content of sulfate (partially water-soluble, ionizable compound) is 2,500 to 200 ppm and more preferably 1,000 to 300 ppm and the content of water-soluble sulfate (water-soluble content of the partially water-soluble, ionizable compound) 750 to 50 ppm.

Bevorzugt beträgt die Restfeuchte der erfindungsgemäßen Diorganylphosphinsäure-Salze 0,01 bis 10 Gew.-%, die Teilchengröße 0,1 bis 1.000 µm und die Schüttdichte 80 bis 800 g/l.The residual moisture of the diorganylphosphinic acid salts according to the invention is preferably from 0.01 to 10% by weight, the particle size from 0.1 to 1000 μm and the bulk density from 80 to 800 g / l.

Bevorzugt beträgt die Löslichkeit der erfindungsgemäßen Diorganylphosphinsäure-Salze in Wasser und/oder organischen Lösungsmitteln zwischen 0,001 und 10 Gew.-%.The solubility of the diorganylphosphinic acid salts according to the invention in water and / or organic solvents is preferably between 0.001 and 10% by weight.

Bevorzugt handelt es sich bei dem Salz des gewünschten Kations weiterhin um Verbindungen mit Anionen aus der Gruppe der Monoorganylphosphinate wie Mono-(C1-18-Alkyl)-Phosphinate, Mono-C6-C10-Aryl)-Phosphinate, Mono-(C1-18-Aralkyl)-Phosphinate, z. B. Monomethylphosphinate, Monoethylphosphinate, Monobutylphosphinate, Monohexylphosphinate, Monophenylphosphinate, Monobenzylphosphinate oder um Verbindungen mit Anionen aus der Gruppe der Monoorganylphosphonate wie Mono-(C1-18-Alkyl)-Phosphonate, Mono-(C6-C10-Aryl)-Phosphonate, Mono-(C1-18-Aralkyl)-Phosphonate, z. B. Monomethylphosphonate, Monoethylphosphonate, Monobutylphosphonate, Monohexylphosphonate, Monophenylphosphonate, Monobenzylphosphonate etc.The salt of the desired cation is preferably also compounds with anions from the group of monoorganylphosphinates, such as mono- (C 1-18 -alkyl) -phosphinates, mono-C 6 -C 10 -aryl phosphonates, and mono- (C 1-10 -alkyl) -phosphinates. C 1-18 aralkyl) phosphinates, e.g. Monomethylphosphinates, monoethylphosphinates, monobutylphosphinates, monohexylphosphinates, monophenylphosphinates, monobenzylphosphinates or compounds containing anions from the group of monoorganylphosphonates such as mono- (C 1-18 -alkyl) -phosphonates, mono- (C 6 -C 10 -aryl) -phosphonates, Mono (C 1-18 aralkyl) phosphonates, e.g. B. Monomethylphosphonate, Monoethylphosphonate, Monobutylphosphonate, Monohexylphosphonate, Monophenylphosphonate, Monobenzylphosphonate etc.

Bevorzugt handelt es sich bei dem Salz des gewünschten Kations um Salze von protonierten Stickstoffbasen z. B. von Ammoniak, primären, sekundären, tertiären und quartären Aminen, z. B. von Melamin, Harnstoff, Biuret, Guanidin, Alkylguanidin, Arylguanidin, Diphenylguanidin, Biguanid, Allantoin, Acetoguanamin, Benzoguanamin, Tolyltriazol, Benzotriazol, 2-Amino-4-methylpyrimidin, Benzylharnstoff, Ethylendimelamin, Acetylenharnstoff, Hydantoin, Malonsäureamidamidin, Dimethylharnstoff, 5,5-Diphenylhydantoin, N,N'-Diphenylharnstoff, Ethylen-bis-5-triazon, Glycinanhydrid, Tetramethylharnstoff, Triethanolamin, Kondensationsprodukte des Melamins z. B. Melem, Melam oder Melon bzw. höher kondensierten Verbindungen dieses Typs.Preferably, the salt of the desired cation is salts of protonated nitrogen bases, for. Example of ammonia, primary, secondary, tertiary and quaternary amines, eg. Melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, allantoin, acetoguanamine, Benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine, acetyleneurea, hydantoin, malonic acid amidamidine, dimethylurea, 5,5-diphenylhydantoin, N, N'-diphenylurea, ethylene-bis-5-triazone, glycine anhydride, tetramethylurea , Triethanolamine, condensation products of melamine z. As melem, melam or melon or higher condensed compounds of this type.

Die Erfindung betrifft auch die Verwendung der erfindungsgemäßen Diorganylphosphinsäure-Salze als Flammschutzmittel, insbesondere in Polymeren oder in Flammschutzmittel-Zusammensetzungen, insbesondere für Polymere.The invention also relates to the use of the diorganylphosphinic acid salts according to the invention as flame retardants, in particular in polymers or in flame retardant compositions, in particular for polymers.

Besonders bevorzugt enthält bei dieser Verwendung die Flammschutzmittel-Zusammensetzung 95 bis 70 Gew.-% des erfindungsgemäßen Diorganylphosphinsäure-Salzes und 5 bis 30 Gew.-% mindestens eines Additives.Particularly preferably, in this use, the flame retardant composition contains 95 to 70 wt .-% of Diorganylphosphinsäure salt according to the invention and 5 to 30 wt .-% of at least one additive.

Bevorzugt beträgt bei der vorgenannten Verwendung die mittlere Teilchengröße der Flammschutzmittel-Zusammensetzung 0,1 bis 3.000 µm, insbesondere 1 bis 100 µm.In the above-mentioned use, the mean particle size of the flame retardant composition is preferably from 0.1 to 3,000 μm, in particular from 1 to 100 μm.

Bevorzugt beträgt bei der vorgenannten Verwendung die Restfeuchte der Flammschutzmittel-Zusammensetzung 0,01 bis 10 Gew.-%, bevorzugt 0,1 bis 1 Gew.-%.In the case of the abovementioned use, the residual moisture of the flame retardant composition is preferably from 0.01 to 10% by weight, preferably from 0.1 to 1% by weight.

Die Erfindung betrifft auch die Verwendung der erfindungsgemäßen Diorganylphosphinsäure-Salzen in oder zur Herstellung von flammgeschützten Polymerformmassen.The invention also relates to the use of the diorganylphosphinic salts according to the invention in or for the production of flame-retardant polymer molding compositions.

Bevorzugt enthält bei dieser Verwendung die flammgeschützte Polymerformmasse 1 bis 50 Gew.-% erfindungsgemäße Diorganylphosphinsäure-Salze, 1 bis 99 Gew.-% Polymer oder Mischungen derselben.Preferably, in this use, the flame-retardant polymer molding composition contains 1 to 50 wt .-% diorganylphosphinic according to the invention salts, 1 to 99 wt .-% polymer or mixtures thereof.

Bevorzugt enthält bei dieser Verwendung die flammgeschützte Polymerformmasse 1 bis 50 Gew.-% erfindungsgemäße Diorganylphosphinsäure-Salze, 1 bis 99 Gew.-% Polymer oder Mischungen derselben und 0,1 bis 60 Gew.-% Additive.In this use, the flame-retardant polymer molding composition preferably comprises 1 to 50% by weight of diorganylphosphinic acid salts according to the invention, 1 to 99% by weight of polymer or mixtures thereof and 0.1 to 60% by weight of additives.

Bevorzugt entstammen dabei die Polymere aus der Gruppe der thermoplastischen Polymere wie Polyester, Polystyrol oder Polyamid und/oder der duroplastischen Polymere.Preferably, the polymers come from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the thermosetting polymers.

Bevorzugt wurde bei dieser Verwendung die Polymerformmasse erhalten, indem die Diorganylphosphinsäure-Salze und/oder die Flammschutzmittel-Zusammensetzungen mit dem Polymergranulat und evtl. Additiven in einem Mischer vermischt, in einem Compoundieraggregat unter höheren Temperaturen in der Polymerschmelze homogenisiert werden und anschließend der homogenisierte Polymerstrang abgezogen, gekühlt und portioniert wird.In this use, the polymer molding composition was preferably obtained by mixing the diorganylphosphinic acid salts and / or the flame retardant compositions with the polymer granules and any additives in a mixer, homogenizing them in a compounding unit at elevated temperatures in the polymer melt and then stripping off the homogenized polymer strand , cooled and portioned.

Geeignete Compoundieraggregate sind Einwellenextruder, Mehrzonenschnecken oder Doppelschneckenextruder.Suitable compounding units are single-screw extruders, multi-zone screws or twin-screw extruders.

Bevorzugt enthalten die flammgeschützten Polymerformkörper, -Filme, -Fäden und -Fasern 1 bis 50 Gew.- % erfindungsgemäße Diorganylphosphinsäure-Salze, 1 bis 99 Gew.-% Polymer oder Mischungen derselben, 0,1 bis 60 Gew.-% Additive und 0,1 bis 60 Gew.-% Füllstoff bzw. Verstärkungsmaterialien.The flame-retardant polymer shaped bodies, films, threads and fibers preferably comprise 1 to 50% by weight of diorganylphosphinic acid salts according to the invention, 1 to 99% by weight of polymer or mixtures thereof, 0.1 to 60% by weight of additives and 0 , 1 to 60 wt .-% filler or reinforcing materials.

Bevorzugt enthalten die flammgeschützten Polymerformkörper, -Filme, -Fäden und -Fasern 1 bis 70 Gew.-% erfindungsgemäße Flammschutzmittel-Zusammensetzung oder erfindungsgemäße flammgeschützte Polymerformmasse, 1 bis 99 Gew.-% Polymer oder Mischungen derselben, 0,1 bis 60 Gew.-% Additive und 0,1 bis 60 Gew.-% Füllstoff bzw. Verstärkungsmaterialien.The flame-retardant polymer moldings, films, filaments and fibers preferably comprise from 1 to 70% by weight of flameproofing composition according to the invention or flameproofed polymer molding composition according to the invention, from 1 to 99% by weight of polymer or mixtures thereof, from 0.1 to 60% by weight. % Additives and 0.1 to 60% by weight of filler or reinforcing materials.

Bevorzugt betragen bei den Verfahren zur Herstellung von den o. g. Polymerformmassen die Verarbeitungstemperaturen bei Polystyrol 170 bis 200 °C, Polypropylen 200 bis 300 °C, Polyethylenterephthalat (PET) 250 bis 290 °C, Polybutylenterephthalat (PBT) 230 bis 270 °C, Polyamid 6 (PA 6)260 bis 290 °C, Polyamid 6.6 (PA 6.6) 260 bis 290 °C, Polycarbonat 280 bis 320 °C.Preferably, in the processes for the preparation of the o. G. Polymer molding compositions the processing temperatures at polystyrene 170 to 200 ° C, polypropylene 200 to 300 ° C, polyethylene terephthalate (PET) 250 to 290 ° C, polybutylene terephthalate (PBT) 230 to 270 ° C, polyamide 6 (PA 6) 260 to 290 ° C, Polyamide 6.6 (PA 6.6) 260 to 290 ° C, polycarbonate 280 to 320 ° C.

Bevorzugt wird beim Verfahren zur Herstellung von flammgeschützten Polymerformkörpern eine flammgeschützte Polymer-Formmassen durch Spritzgießen und Pressen, Schaumspritzgießen, Gasinnendruck-Spritzgießen, Blasformen, Foliengießen, Kalandern, Laminieren, Beschichten etc. zum flammgeschützten Polymerformkörper verarbeitet.In the process for the preparation of flame-retardant polymer moldings, a flame-retardant polymer molding compound is preferred by injection molding and pressing, foam injection molding, internal gas pressure injection molding, Blow molding, film casting, calendering, laminating, coating, etc. processed to the flame-retardant polymer molding.

Die Verarbeitungstemperaturen bei dem vorgenannten Verfahren betragen bei Polystyrol 200 bis 250 °C, bei Polypropylen 200 bis 300 °C, bei Polyethylenterephthalat (PET) 250 bis 290 °C, bei Polybutylenterephthalat (PBT) 230 bis 270 °C, bei Polyamid 6 (PA 6) 260 bis 290 °C, bei Polyamid 6.6 (PA 6.6) 6.6 260 bis 290 °C, bei Polycarbonat 280 bis 320 °C betragen.The processing temperatures in the above-mentioned method are 200 to 250 ° C in the case of polystyrene, 200 to 300 ° C. in the case of polypropylene, 250 to 290 ° C. in the case of polyethylene terephthalate (PET), 230 to 270 ° C. in the case of polybutylene terephthalate (PBT), and 6 to polyamide 6 (PA 6) 260 to 290 ° C, in the case of polyamide 6.6 (PA 6.6) 6.6 260 to 290 ° C, in the case of polycarbonate 280 to 320 ° C.

Die Verträglichkeit eines Additivs mit einem Polymer kann sich darin ausdrücken, wie sehr das mittlere Molekulargewicht bei der Verarbeitung eines Polymers durch das Additiv verringert wird. Man vergleicht dazu eine für das mittlere Molekulargewicht charakteristische Kennzahl des unbehandelten Polymers mit der Kennzahl des mit Additiv behandelten Polymers. Eine solche dimensionslose Kennzahl ist die spezifische Viskosität (SV-Wert). Diese leitet sich aus der Bestimmung der Viskosität einer Lösung des Polymers in einem Lösungsmittel her. Dabei wird die Viskosität der Polymerlösung zu der Viskosität des reinen Lösungsmittels ins Verhältnis gesetzt.The compatibility of an additive with a polymer can be expressed in terms of how much the average molecular weight is reduced in the processing of a polymer by the additive. A characteristic of the untreated polymer characteristic of the average molecular weight is compared with the characteristic number of the additive-treated polymer. One such dimensionless index is the specific viscosity (SV value). This is derived from the determination of the viscosity of a solution of the polymer in a solvent. The viscosity of the polymer solution is set in relation to the viscosity of the pure solvent.

Die Verträglichkeit wird mit Hilfe der SV-Zahl ausgedrückt. Danach verbessert sich die Verträglichkeit (SV-Zahl) z. B. mit Polybutylenterephthalat ab einem bestimmten Gehalt an teilweise wasserlöslichen ionisierbaren Verbindungen sprunghaft.The compatibility is expressed by the SV number. After that, the compatibility (SV number) improves z. B. with polybutylene terephthalate from a certain content of partially water-soluble ionizable compounds leaps and bounds.

Erfindungsgemäß sind bei Polybutylenterephthalat SV-Zahlen von 750 bis 1400 bevorzugt, 850 bis 1250 besonders bevorzugt. Die SV-Zahl kann von einer erfindungsgemäßen Polymer-Formmasse oder von einem Polymerformkörper bestimmt werden.According to the invention, in the case of polybutylene terephthalate, SV numbers of from 750 to 1400 are preferred, and from 850 to 1250 are particularly preferred. The SV number can be determined by a polymer molding composition according to the invention or by a polymer molding.

Zur Beurteilung der Verträglichkeit kann auch der Volumenfließindex (Melt Flow Index, MFI, MVR) herangezogen werden. Ein starker Anstieg des MVR-Wertes deutet auf Polymerabbau hin.To assess the compatibility, the volume flow index (Melt Flow Index, MFI, MVR) can also be used. A strong increase in the MVR value indicates polymer degradation.

Bei erfindungsgemäßen glasfaserverstärkten flammgeschützten Polymerformmassen auf Basis von Polyamid 6.6 beträgt der Wert 2 bis 200 cm3/min (275 °C, 5 kg).In the case of glass fiber-reinforced flame-retardant polymer molding compositions based on polyamide 6.6 according to the invention, the value is from 2 to 200 cm 3 / min (275 ° C., 5 kg).

Bei den teilweise wasserlöslichen, ionisierbaren Verbindungen handelt es sich z. B. um Substanzen aus der Gruppe der anorganischen, organischen, insbesondere auch phosphororganischen Salzen und Mischungen davon.The partially water-soluble, ionizable compounds are, for. B. to substances from the group of inorganic, organic, especially organophosphorus salts and mixtures thereof.

Bevorzugt sind teilweise wasserlösliche, ionisierbare Verbindungen mit anorganischen Anionen wie z. B. Fluoride, Chloride, Bromide, lodide, Hypohalogenite, Halogenite, Halogenate, lodat, Perhalogenate, Perchlorat, Chalgogenide, Oxide, Hydroxide, Peroxide, Superoxide, Sulfate, Hydrogensulfate, Sulfathydrate, Sulfite, Peroxosulfate, Nitride, Phosphide, Nitrat, Nitrathydrate, Nitrite, Phosphate, Peroxophosphate, Phosphite, Hypophosphite, Pyrophosphate, Carbonate, Hydrogencarbonate, Hydroxidcarbonate, Carbonathydrate, Silicate, Hexafluorosilicate, Hexafluorosilicathydrate, Stannate, Borate, Polyborate, Peroxoborate, Thiocyanate, Cyanate, Cyanide, Chromate, Chromite, Molybdate, Permanganat.Preference is given to partially water-soluble, ionizable compounds with inorganic anions such. B. Fluorides, chlorides, bromides, iodides, hypohalites, halogenites, halogenates, iodate, perhalates, perchlorate, chalcogenides, oxides, hydroxides, peroxides, superoxides, sulfates, hydrogen sulfates, sulfate hydrates, sulfites, peroxosulfates, nitrides, phosphides, nitrate, nitrate hydrates, Nitrites, phosphates, peroxophosphates, phosphites, hypophosphites, pyrophosphates, carbonates, bicarbonates, hydroxide carbonates, carbonate hydrates, silicates, hexafluorosilicates, hexafluorosilicate hydrates, stannates, borates, polyborates, peroxoborates, thiocyanates, cyanates, cyanides, chromates, chromites, molybdate, permanganate.

Bevorzugt sind auch teilweise wasserlösliche, ionisierbare Verbindungen mit organischen Anionen aus der Gruppe der Mono-, Di-, Oligo-, Polycarbonsäuren, z. B. Formiate, Acetate, Acetathydrate, Trifluoracetathydrate, Propionate, Butyrate, Valerate, Caprylate, Oleate, Stearate, Oxalate, Tartrate, Citrate, Citrathydrate, Benzoate, Salicylate, Lactat, Lactathydrate, Acrylsäure, Maleinsäure, Bernsteinsäure, von Aminosäuren (Glyzin), von sauren Hydroxofunktionen (Phenolate etc.), Para-Phenolsulfonate, Para-Phenolsulfonathydrate, Acetylacetonathydrate, Tannate, Dimethyldithiocarbamate, Trifluormethansulfonat, Alkylsulfonate, Aralkylsulfonate.Also partially water-soluble, ionizable compounds with organic anions from the group of mono-, di-, oligo-, polycarboxylic acids, eg. Formates, acetates, acetate hydrates, trifluoroacetate hydrates, propionates, butyrates, valerates, caprylates, oleates, stearates, oxalates, tartrates, citrates, citrate hydrates, benzoates, salicylates, lactate, lactate hydrates, acrylic acid, maleic acid, succinic acid, of amino acids (glycine), of acidic hydroxy functions (phenates etc.), para-phenol sulfonates, para-phenolsulfonate hydrates, acetylacetonate hydrates, tannates, dimethyldithiocarbamates, trifluoromethanesulfonate, alkylsulfonates, aralkylsulfonates.

Bevorzugt sind auch teilweise wasserlösliche, ionisierbare Verbindungen mit Anionen aus der Gruppe der Monoorganylphosphinate wie Mono-(C1-18-Alkyl)-Phosphinate, Mono-(C6-C10-Aryl)-Phosphinate, Mono-(C1-18-Aralkyl)-Phosphinate z. B. Monomethylphosphinate Monoethylphosphinate, Monobutylphosphinate, Monohexylphosphinate, Monophenylphosphinate, Monobenzylphosphinate etc. oder mit Anionen aus der Gruppe der Monoorganylphosphonate wie Mono-(C1-18-Alkyl)-Phosphonate, Mono-C6-C10-Aryl)-Phosphonate, Mono-(C1-18-Aralkyl)-Phosphonate z. B. Monomethylphosphonate Monoethylphosphonate, Monobutylphosphonate, Monohexylphosphonate, Monophenylphosphonate, Monobenzylphosphonate etc.And partially water-soluble, ionizable compounds having anions from the group of Monoorganylphosphinate such as mono- (C 1-18 alkyl) -phosphinates, mono- (C 6 -C 10 aryl) -phosphinates, mono- are preferred (C: 1 - 18 -Aralkyl) phosphinates z. As monomethylphosphinates Monoethylphosphinate, Monobutylphosphinate, Monohexylphosphinate, Monophenylphosphinate, Monobenzylphosphinate etc. or with anions from the group of Monoorganylphosphonate such as mono- (C 1 - 18 alkyl) phosphonates, mono-C 6 -C 10 aryl) phosphonates, mono - (C 1 - 18 aralkyl) phosphonates z. B. Monomethylphosphonate Monoethylphosphonate, Monobutylphosphonate, Monohexylphosphonate, Monophenylphosphonate, Monobenzylphosphonate etc.

Weiterhin sind auch beliebige Mischungen erfindungsgemäß einsetzbar. Bevorzugt sind teilweise wasserlösliche, ionisierbare Verbindungen mit Kationen der Alkalimetalle sowie mit Kationen von protonierten Stickstoffbasen z. B. von Ammoniak, primären, sekundären, tertiären und quartären Aminen.Furthermore, any mixtures can be used according to the invention. Preference is given to partially water-soluble, ionizable compounds with cations of the alkali metals and with cations of protonated nitrogen bases z. Example of ammonia, primary, secondary, tertiary and quaternary amines.

Bevorzugt sind teilweise wasserlösliche, ionisierbare Verbindungen mit Kationen von protonierten Stickstoffbasen z. B. von Melamin, Harnstoff, Guanidin, Alkylguanidin, Arylguanidin, Diphenylguanidin, Biguanid, Biuret, Allantoin, Acetoguanamin, Benzoguanamin, Tolyltriazol, Benzotriazol, 2-Amino-4-methylpyrimidin, Benzylharnstoff, Ethylendimelamin, Acetylenharnstoff, Hydantoin, Malonsäureamidamidin, Dimethylharnstoff, 5,5-Diphenylhydantoin, N,N'-Diphenylharnstoff, Ethylen-bis-5-triazon, Glycinanhydrid, Tetramethylharnstoff, Triethanolamin, Kondensationsprodukte des Melamins, z. B. Melem, Melam oder Melon bzw. höher kondensierte Verbindungen dieses Typs.Preference is given to partially water-soluble, ionizable compounds with cations of protonated nitrogen bases z. Melamine, urea, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, biuret, allantoin, acetoguanamine, benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine, acetyleneurea, hydantoin, malonic acid amidamidine, dimethylurea, 5 , 5-diphenylhydantoin, N, N'-diphenylurea, ethylene-bis-5-triazone, glycine anhydride, tetramethylurea, triethanolamine, condensation products of melamine, e.g. As melem, melam or melon or higher condensed compounds of this type.

Bevorzugt sind teilweise wasserlösliche, ionisierbare Verbindungen mit Kationen der Erdalkalimetalle; mit Kationen der Elemente der dritten Hauptgruppe; mit Kationen der Nebengruppenelemente. Besonders bevorzugt sind dabei Titan, Eisen, Zink.Preference is given in part to water-soluble, ionizable compounds with cations of the alkaline earth metals; with cations of the elements of the third main group; with cations of the subgroup elements. Particularly preferred are titanium, iron, zinc.

Der Gehalt an teilweise ionisierbaren Verbindungen folgt aus der Herstellung des Diorganylphosphinsäure-Salzes. Quellen können z. B. das Lösungsmittel und/oder die Ausgangsverbindungen sein.The content of partially ionizable compounds follows from the preparation of Diorganylphosphinsäure salt. Sources can z. B. be the solvent and / or the starting compounds.

Der Gehalt an teilweise ionisierbaren Verbindungen ist dabei differenziert zu betrachten. Zunächst ist der gesamte im Metall-Diorganylphosphinat vorhandene Gehalt (Gesamt-Gehalt) wichtig. Bevorzugt sind Gesamt-Gehalte von 8.200 bis 100 ppm, besonders bevorzugt 7.000 bis 200 ppm.The content of partially ionizable compounds is to be considered differentiated. First, the total content present in the metal diorganophosphinate (total content) is important. Total contents of from 8,200 to 100 ppm, more preferably 7,000 to 200 ppm, are preferred.

Es wurde nun überraschend gefunden, dass sich nur ein Teil der ionisierbaren Verbindungen durch wässrige Extraktion aus dem Diorganylphosphinsäure-Salz entfernen lässt (wasserlöslicher Anteil an ionisierbaren Verbindungen). Der verbleibende Rest, d. h. die Differenz zwischen Gesamt-Gehalt an teilweise ionisierbaren Verbindungen und wasserlöslichem Anteil an ionisierbaren Verbindungen ist auch durch wiederholtes Auswaschen nicht aus dem Diorganylphosphinsäure-Salz extrahierbar. Da es sich bei den vorliegenden Diorganylphosphinsäure-Salzen um polymere Koordinationsverbindungen handelt, können Anionen als Metallphosphinate, Metallhydroxophosphinate bzw. Metallhydroxosalze gebunden sein.It has now surprisingly been found that only part of the ionizable compounds can be removed from the diorganylphosphinic acid salt by aqueous extraction (water-soluble fraction of ionizable compounds). The remainder, ie the difference between total content of partially ionizable compounds and water-soluble fraction of ionizable Compounds can not be extracted from the diorganylphosphinic acid salt by repeated washing. Since the present diorganylphosphinic salts are polymeric coordination compounds, anions can be bound as metal phosphinates, metal hydroxophosphinates or metal hydroxo salts.

Bevorzugt sind Gehalte an wasserlöslichen ionisierbaren Verbindungen von 3.200 bis 10 und besonders bevorzugt 2.000 bis 40 ppm.Preference is given to contents of water-soluble ionizable compounds of from 3,200 to 10 and particularly preferably 2,000 to 40 ppm.

Eine Teilchengröße oberhalb des bevorzugten Bereiches erschwert die gleichmäßige Verteilung des erfindungsgemäßen Diorganylphosphinsäure-Salze, eine Teilchengröße unterhalb des bevorzugten Bereiches erschwert die Einarbeitung wegen verstärkter Staubbildung und Explosionsgefahr. Restfeuchten oberhalb der erfindungsgemäß bevorzugten Bereiche bewirken einen verstärkten Polymerabbau.A particle size above the preferred range makes the uniform distribution of the diorganylphosphinic acid salts according to the invention more difficult, a particle size below the preferred range makes incorporation more difficult because of increased dust formation and the risk of explosion. Residual moistures above the inventively preferred ranges cause increased polymer degradation.

Das erfindungsgemäße Aluminiumtrisdiethylphosphinat durchläuft bei 160 bis 200, bevorzugt 175 bis 185 °C eine reversible Kristallumwandlung (aus Röntgenpulverdaten). Eine solche Umwandlung kann bei der Verarbeitung mit Kunststoffen vorteilhaft sein.The Aluminiumtrisdiethylphosphinat invention undergoes at 160 to 200, preferably 175 to 185 ° C, a reversible crystal transformation (from X-ray powder data). Such conversion may be advantageous in processing with plastics.

Die erfindungsgemäßen Diorganylphosphinsäure-Salze haben einen bevorzugten Gehalt an Initiatoren-Endgruppen von 0,0001 bis 10 mol-%, besonders bevorzugt von 0,001 bis 1 mol-%. Initiatoren-Endgruppen können beim Radikal-Kettenabbruch an das letzte Molekül der Radikalkette bei der Addition des Olefins an das Hypophosphit gebunden bleiben.The diorganylphosphinic acid salts according to the invention have a preferred content of initiator end groups of from 0.0001 to 10 mol%, particularly preferably from 0.001 to 1 mol%. Initiator end groups may remain attached to the last molecule of the radical chain during radical chain termination upon addition of the olefin to the hypophosphite.

Die erfindungsgemäßen Diorganylphosphinsäure-Salze haben bevorzugte L-Farbwerte von 85 bis 99,9, besonders bevorzugt 90 bis 98.The diorganylphosphinic acid salts according to the invention have preferred L color values of 85 to 99.9, more preferably 90 to 98.

Die erfindungsgemäßen Diorganylphosphinsäure-Salze haben bevorzugte a-Farbwerte von -4 bis +9, besonders bevorzugt -2 bis +6.The diorganylphosphinic acid salts of the invention have preferred a color values of from -4 to +9, more preferably from -2 to +6.

Die erfindungsgemäßen Diorganylphosphinsäure-Salze haben bevorzugte b-Farbwerte von -2 bis +6, besonders bevorzugt -1 bis +3.The diorganylphosphinic acid salts of the invention have preferred b color values of from -2 to +6, more preferably from -1 to +3.

Die Farbwerte werden im System nach Hunter (CIE-LAB-System, Commission Internationale d'Eclairage) angegeben.The color values are specified in the Hunter system (CIE-LAB system, Commission Internationale d'Eclairage).

Diorganylphosphinsäure-Salze mit L-Werten unterhalb bzw. mit a- bzw. b-Werten außerhalb des erfindungsgemäßen Bereiches erfordern einen höheren Weißpigmenteinsatz. Dieser verschlechtert die mechanischen Stabilitätseigenschaften des Polymerformkörpers (z. B. E-Modul).Diorganylphosphinic acid salts with L values below or with a or b values outside the range according to the invention require a higher use of white pigment. This deteriorates the mechanical stability properties of the polymer molding (eg modulus of elasticity).

Die erfindungsgemäßen Diorganylphosphinsäure-Salze zeigen verbesserte Verträglichkeit bei einer Vielfalt von Polymeren, die in erfindungsgemäßen flammgeschützten Polymerformmassen bzw. erfindungsgemäßen flammgeschützten Polymerformkörpern eingesetzt werden, z. B. bei Polyolefinen, Polystyrolen und Polystyrol-Copolymeren, Polyacrylaten und Polymethacrylaten, Vinyl- und Allyl-Polymeren, Homo- und Co-Polymeren von ungesättigten Alkoholen, Polyacetale, Polyphenylensulfide, Polyamide und Co-Polyamide, Polyester, Polycarbonate.The diorganylphosphinic acid salts according to the invention show improved compatibility with a variety of polymers which are used in flameproofed polymer molding compositions according to the invention or flameproofed polymer moldings according to the invention, e.g. As in polyolefins, polystyrenes and polystyrene copolymers, polyacrylates and polymethacrylates, vinyl and allyl polymers, homo- and co-polymers of unsaturated alcohols, polyacetals, polyphenylene sulfides, polyamides and co-polyamides, polyesters, polycarbonates.

Erfindungsgemäß wird das Diorganylphosphinsäure-Salz hergestellt, indem man die Diorganylphosphinsäure mit elementarem Metall, oder einem Metallsalz 0,01 bis 1 Stunden bei 0 bis 300 °C umsetzt. Bevorzugte Metallsalze sind dabei Metalloxide, gemischte Metall-Oxid-Hydroxide, Hydroxide etc.According to the invention, the diorganylphosphinic acid salt is prepared by reacting the diorganylphosphinic acid with elemental metal, or a metal salt for 0.01 to 1 hours at 0 to 300 ° C. Preferred metal salts are metal oxides, mixed metal oxide hydroxides, hydroxides, etc.

In einer anderen erfindungsgemäßen Ausführungsform wird das Diorganylphosphinsäure-Salz hergestellt, indem man die Diorganylphosphinsäure mit einer freien Base 0,01 bis 1 Stunden bei 0 bis 300 °C umsetzt.In another embodiment of the invention, the diorganylphosphinic acid salt is prepared by reacting the diorganylphosphinic acid with a free base at 0 to 300 ° C for 0.01 to 1 hours.

In einer anderen Ausführungsform wird das erfindungsgemäße Diorganylphosphinsäure-Salz hergestellt, indem man die Diorganylphosphinsäure in Form eines Alkalimetall-Salzes mit einem Salz des gewünschten Kations 0,01 bis 1 Stunden bei 0 bis 300 °C umsetzt.In another embodiment, the diorganylphosphinic acid salt of the invention is prepared by reacting the diorganylphosphinic acid in the form of an alkali metal salt with a salt of the desired cation at 0 to 300 ° C for from 0.01 to 1 hour.

Bevorzugte Salze, die die gewünschten Kationen liefern, sind dabei Acetate, Hydroxoacetate, Chloride, Hydroxochloride, Nitrate, Sulfate, Hydroxosulfate.Preferred salts which provide the desired cations are acetates, hydroxoacetates, chlorides, hydroxochlorides, nitrates, sulfates, hydroxosulfates.

Bevorzugt ist deren Konzentration in der wässrigen Lösung 5 bis 95 Gew.-% (wasserfreier Feststoff), besonders bevorzugt 20 bis 50 Gew.-%.Their concentration in the aqueous solution is preferably from 5 to 95% by weight (anhydrous solid), more preferably from 20 to 50% by weight.

Alkalimetall-Diorganylphosphinsäure-Salze sind in wasserfreier, hydratisierter oder gelöster Form bevorzugt. Diese erfindungsgemäßen Alkalimetall-Diorganylphosphinsäure-Salze haben in Wasser und/oder den üblichen organischen Lösungsmitteln eine bevorzugte Löslichkeit zwischen 1 und 70 Gew.-% (wasserfreier Feststoff).Alkali metal diorganophosphinic acid salts are preferred in anhydrous, hydrated or dissolved form. These alkali metal Diorganylphosphinsäure salts according to the invention have a preferred solubility in water and / or the usual organic solvents between 1 and 70 wt .-% (anhydrous solid).

Die erfindungsgemäßen Diorganylphosphinsäure-Salze des gewünschten Kations haben in Wasser und/oder den üblichen organischen Lösungsmitteln eine bevorzugte Löslichkeit zwischen 0,001 und 10 Gew.-% (wasserfreier Feststoff).The diorganylphosphinic acid salts of the desired cation according to the invention have a preferred solubility in water and / or the customary organic solvents of between 0.001 and 10% by weight (anhydrous solid).

In einer anderen Ausführungsform wird das erfindungsgemäße Diorganylphosphinsäure-Salz hergestellt, indem man eine Diorganylphosphinsäure in Form eines reaktiven Derivates mit einem Derivat des gewünschten Kations 0,01 bis 1 Stunde bei 0 bis 300 °C umsetzt. Bevorzugte Diorganylphosphinsäurederivate sind Diorganylphosphinsäureester, -pyroester, -chloride, -phosphate, -acetate, -phenolate etc.In another embodiment, the diorganylphosphinic acid salt of the invention is prepared by reacting a diorganylphosphinic acid in the form of a reactive derivative with a derivative of the desired cation for 0.01 to 1 hour at 0 to 300 ° C. Preferred diorganylphosphinic acid derivatives are diorganylphosphinic acid esters, pyroesters, chlorides, phosphates, acetates, phenolates, etc.

Die Erfindung betrifft auch die Anwendung der erfindungsgemäßen Diorganylphosphinsäure-Salze als Flammschutzmittel und in Flammschutzmittel-Zusammensetzungen. Dazu werden sie bevorzugt gemeinsam mit anderen Additiven eingesetzt.The invention also relates to the use of the diorganylphosphinic acid salts of the invention as flame retardants and in flame retardant compositions. For this purpose, they are preferably used together with other additives.

Bevorzugt enthält die erfindungsgemäße Flammschutzmittel-Zusammensetzung:

  1. 1) 30 bis 99,9 Gew.-% eines erfindungsgemäßen Diorganylphosphinsäure-Salzes
  2. 2) 0,1 bis 50 % mindestens eines Additives.
The flame retardant composition according to the invention preferably comprises:
  1. 1) 30 to 99.9 wt .-% of a Diorganylphosphinsäure invention salt
  2. 2) 0.1 to 50% of at least one additive.

Besonders bevorzugt enthält die erfindungsgemäße Flammschutzmittel-Zusammensetzung 95 bis 70 Gew.-% eines erfindungsgemäßen Diorganylphosphinsäure-Salzes und 5 bis 30 % mindestens eines Additives Bevorzugte weitere Additive in Flammschutzmittel-Zusammensetzungen sind z. B. Synergisten wie in DE-A-2827867 , DE-A-19933901 , DE-A-19614424 , DE-A-19734437 beschrieben.The flame retardant composition according to the invention particularly preferably contains 95 to 70% by weight of a diorganylphosphinic acid salt according to the invention and 5 to 30% of at least one additive Preferred further additives in flame retardant compositions are e.g. B. synergists as in DE-A-2827867 . DE-A-19933901 . DE-A-19614424 . DE-A-19734437 described.

Erfindungsgemäß werden als Synergisten Melaminphosphat (z. B. Melapur® MP der Fa. Ciba-DSM Melapur), Dimelaminphosphat, Pentamelamintriphosphat, Trimelamindiphosphat, Tetrakismelamintriphosphat, Hexakismelaminpentaphosphat, Melamindiphosphat, Melamintetraphosphat, Melaminpyrophosphat, Melaminpolyphosphate, Melampolyphosphate, Melempolyphosphate und/oder Melonpolyphosphate oder Mischungen davon bevorzugt.As synergists melamine phosphate (for. Example Melapur ® MP of Messrs. Ciba-DSM Melapur) According to the invention, dimelamine phosphate, Pentamelamintriphosphat, Trimelamindiphosphat, Tetrakismelamintriphosphat, Hexakismelaminpentaphosphat, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphates, Melampolyphosphate, Melempolyphosphate and / or melon polyphosphates or mixtures thereof prefers.

Weiterhin sind Kondensationsprodukte des Melamins (z. B. Melam, Melem und/oder Melon) oder Umsetzungsprodukte des Melamins mit Phosphorsäure bzw.Furthermore, condensation products of melamine (eg melam, melem and / or melon) or reaction products of melamine with phosphoric acid or

Umsetzungsprodukte von Kondensationsprodukten des Melamins mit Phosphorsäure sowie Gemische der genannten Produkte bevorzugt ( WO-96/16948 ). Unter den Umsetzungsprodukten mit Phosphorsäure versteht man Verbindungen, die durch Umsetzung von Melamin oder den kondensierten Melaminverbindungen wie Melam, Melem oder Melon etc. mit Phosphorsäure entstehen. Beispiele hierfür sind Melaminpolyphosphat, Melampolyphosphat und Melempolyphosphat bzw. gemischte Polysalze ( WO-98/39306 , WO-98/45364 , WO-98/08898 ).Reaction products of condensation products of melamine with phosphoric acid and mixtures of the said products are preferred ( WO-96/16948 ). The reaction products with phosphoric acid are compounds which are formed by reacting melamine or the condensed melamine compounds such as melam, melem or melon, etc., with phosphoric acid. Examples of these are melamine polyphosphate, melampolyphosphate and melem polyphosphate or mixed polysalts ( WO-98/39306 . WO-98/45364 . WO-98/08898 ).

Erfindungsgemäß sind als Synergisten weiterhin bevorzugt oligomere Ester des Tris(hydroxyethyl)isocyanurats mit aromatischen Polycarbonsäuren, Benzoguanamin, Tris(hydroxyethyl)isocyanurat, Allantoin, Glycouril, Melamin, Melaminkondensationsprodukte wie Melam, Melem und/oder Melon, Melamincyanurat, Dicyandiamid und/oder Guanidin.Also preferred according to the invention as synergists are oligomeric esters of tris (hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine condensation products such as melam, melem and / or melon, melamine cyanurate, dicyandiamide and / or guanidine.

Erfindungsgemäß sind als Synergisten weiterhin bevorzugt stickstoffhaltige Phosphate der Formeln (NH4)yH3-yPO4 bzw. (NH4PO3)z, mit y gleich 1 bis 3 und z gleich 1 bis 10.000.Nitrogen-containing phosphates of the formulas (NH 4 ) yH 3 -yPO 4 or (NH 4 PO 3 ) z, where y is 1 to 3 and z is 1 to 10 000, are furthermore preferred according to the invention as synergists.

Erfindungsgemäß sind als Synergisten Stickstoffverbindungen bevorzugt, z. B. solche der Formeln (III) bis (VIII) oder Gemische davon

Figure imgb0002
Figure imgb0003
Figure imgb0004
 worin

R5 bis R7
Wasserstoff, C1-C8-Alkyl, C5-C16-Cycloalkyl oder -Alkylcycloalkyl, möglicherweise substituiert mit einer Hydroxy- oder einer C1-C4-Hydroxyalkyl-Funktion, C2-C8-Alkenyl, C1-C8-Alkoxy, -Acyl, -Acyloxy, C6-C12-Aryl oder -Arylalkyl, -OR8 und -N(R8)R9, sowie N-alicyclisch oder N-aromatisch,
R8
Wasserstoff, C1-C8-Alkyl, C5-C16-Cycloalkyl oder -Alkylcycloalkyl, möglicherweise substituiert mit einer Hydroxy- oder einer C1-C4-Hydroxyalkyl-Funktion, C2-C8-Alkenyl, C1-C8-Alkoxy, -Acyl, -Acyloxy oder C6-C12-Aryl oder -Arylalkyl,
R9 bis
R13 die gleichen Gruppen wie R8 sowie -O-R8, m und n unabhängig voneinander 1, 2, 3 oder 4 und
X
Säuren, die Addukte mit Triazinverbindungen (III) bilden können,
bedeuten.Nitrogen compounds are preferred according to the invention as synergists, eg. B. those of the formulas (III) to (VIII) or mixtures thereof
Figure imgb0002
Figure imgb0003
Figure imgb0004
 wherein
R 5 to R 7
Is hydrogen, C 1 -C 8 -alkyl, C 5 -C 16 -cycloalkyl or -alkylcycloalkyl, possibly substituted by a hydroxy or by a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 - C 8 alkoxy, acyl, acyloxy, C 6 -C 12 aryl or arylalkyl, -OR 8 and -N (R 8 ) R 9 , as well as N-alicyclic or N-aromatic,
R 8
Is hydrogen, C 1 -C 8 -alkyl, C 5 -C 16 -cycloalkyl or -alkylcycloalkyl, possibly substituted by a hydroxy or by a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 - C 8 alkoxy, acyl, acyloxy or C 6 -C 12 aryl or arylalkyl,
R 9 to
R 13 is the same groups as R 8 and -OR 8 , m and n are independently 1, 2, 3 or 4 and
X
Acids that can form adducts with triazine compounds (III),
mean.

Bevorzugte weitere Additive in Flammschutzmittel-Zusammensetzungen sind nach EP-A-1024167 Sauerstoffverbindungen des Siliciums, Magnesiumverbindungen, Metallcarbonate von Metallen der zweiten Hauptgruppe des Periodensystems, roter Phosphor, Zink- oder Aluminiumverbindungen.Preferred further additives in flame retardant compositions are according to EP-A-1024167 Oxygen compounds of silicon, magnesium compounds, metal carbonates of metals of the second main group of the periodic table, red phosphorus, zinc or aluminum compounds.

Bevorzugte weitere Additive in Flammschutzmittel-Zusammensetzungen sind Oxide, Hydroxide, Carbonate, Silikate, Borate, Stannate, gemischte Oxid-Hydroxide, Oxid-Hydroxid-Carbonate, Hydroxid-Silikate oder Hydroxid-Borate oder Mischungen davon.Preferred further additives in flame retardant compositions are oxides, hydroxides, carbonates, silicates, borates, stannates, mixed oxide hydroxides, oxide-hydroxide-carbonates, hydroxide-silicates or hydroxide-borates or mixtures thereof.

Bevorzugte weitere Additive in Flammschutzmittel-Zusammensetzungen sind Magnesiumoxid, Magnesiumhydroxid, Hydrotalcite, Dihydrotalcit, Magnesium-Carbonate oder Magnesium-Calcium-Carbonate; Calciumhydroxid, Calciumoxid und Hydrocalumit; Zinkoxid, Zinkhydroxid, Zinnoxidhydrat, Zinkcarbonat, -stannat, -hydroxystannat, basisches Zink-Silikat, -phosphat, -borat, -molybdate oder -sulfide; Aluminiumoxid, Aluminiumhydroxid, Böhmit, Gibbsit oder Aluminiumphosphat, Manganoxid, Manganhydroxid, Zinnoxid; Carbodiimide und/oder (Poly-)isocyanate.Preferred further additives in flame retardant compositions are magnesium oxide, magnesium hydroxide, hydrotalcites, dihydrotalcite, magnesium carbonates or magnesium calcium carbonates; Calcium hydroxide, calcium oxide and hydrocalumite; Zinc oxide, zinc hydroxide, tin oxide hydrate, zinc carbonate, stannate, hydroxystannate, basic zinc silicate, phosphate, borate, molybdate or sulfides; Alumina, aluminum hydroxide, boehmite, gibbsite or aluminum phosphate, manganese oxide, manganese hydroxide, tin oxide; Carbodiimides and / or (poly) isocyanates.

Bevorzugte weitere Additive in Flammschutzmittel-Zusammensetzungen sind Carbonylbiscaprolactam oder Styrol-Acryl-Polymere; sterisch gehinderte Phenole, sterisch gehinderte Amine und Lichtstabilisatoren, Phosphonite, Antioxidantien und Trennmittel.Preferred further additives in flame retardant compositions are carbonylbiscaprolactam or styrene-acrylic polymers; hindered phenols, hindered amines and light stabilizers, phosphonites, antioxidants and release agents.

Bevorzugt wird das erfindungsgemäße Diorganylphosphinsäure-Salz in konfektionierter Form (gecoated, staubreduziert, schmelzgranuliert und/oder tropfgranuliert, kompaktiert, sprühgranuliert, dispergiert, Pastenform u. a.) in Flammschutzformulierungen eingesetzt.The diorganylphosphinic acid salt according to the invention is preferably used in ready-to-use form (coated, reduced in dust, melt-granulated and / or drop-granulated, compacted, spray-granulated, dispersed, paste form and the like) in flame retardant formulations.

Die mittlere Teilchengröße der erfindungsgemäßen Flammschutzmittel-Zusammensetzungen beträgt 0,1 bis 3.000 µm.The average particle size of the flame retardant compositions of the invention is 0.1 to 3000 microns.

Eine Teilchengröße oberhalb des bevorzugten Bereiches erschwert die gleichmäßige Verteilung des erfindungsgemäßen Diorganylphosphinsäure-Salzes, eine Teilchengröße unterhalb des bevorzugten Bereiches erschwert die Einarbeitung wegen verstärkter Staubbildung und Explosionsgefahr.A particle size above the preferred range makes the uniform distribution of the diorganylphosphinic acid salt according to the invention more difficult, a particle size below the preferred range makes incorporation more difficult because of increased dust formation and the risk of explosion.

Die bevorzugte Schüttdichte des erfindungsgemäßen Flammschutzmittel-Zusammensetzung beträgt 80 bis 1500 g/l, besonders bevorzugt 200 bis 1000 g/l; in einer anderen Ausführungsform 80 bis 800 g/l, besonders bevorzugt 200 bis 700 g/l und einer weiteren Ausführungsform 200 bis 1500 g/l, bevorzugt 300 bis 1000 g/l.The preferred bulk density of the flame retardant composition of the invention is 80 to 1500 g / l, more preferably 200 to 1000 g / l; in another embodiment 80 to 800 g / l, more preferably 200 to 700 g / l and another embodiment 200 to 1500 g / l, preferably 300 to 1000 g / l.

Insbesondere betrifft die Erfindung die Anwendung der erfindungsgemäßen Diorganylphosphinsäure-Salze und/oder der Flammschutzmittel-Zusammensetzungen in flammgeschützten Polymerformmassen enthaltend Polymer. Erfindungsgemäß bevorzugte Polymere sind thermoplastische wie z. B. wie Polyester, Polystyrol oder Polyamid und/oder duroplastische Polymere Bevorzugt enthält die flammgeschützte Polymerformmasse 1 bis 50 Gew.-% erfindungsgemäße Diorganylphosphinsäure-Salze oder erfindungsgemäße Flammschutzmittel-Zusammensetzung 1 bis 99 Gew.-% Polymer oder Mischungen derselben 0 bis 60 Gew.-% Additive.In particular, the invention relates to the use of the diorganylphosphinic acid salts according to the invention and / or the flame retardant compositions in flame-retardant polymer molding compositions containing polymer. According to preferred polymers are thermoplastic such. Example, such as polyester, polystyrene or polyamide and / or thermoset polymers Preferably, the flame-retardant polymer molding composition 1 to 50 wt .-% diorganylphosphinic according to the invention salts or inventive flame retardant composition 1 to 99 wt .-% polymer or mixtures thereof 0 to 60 wt. -% additives.

Besonders bevorzugt enthält die flammgeschützte Polymerformmasse 5 bis 30 Gew.-% erfindungsgemäße Diorganylphosphinsäure-Salze oder erfindungsgemäße Flammschutzmittel-Zusammensetzung,
5 bis 90 Gew.-% Polymer oder Mischungen derselben
5 bis 40 Gew.-% Additive
5 bis 40 Gew.-% Füllstoff bzw. Verstärkungsmaterialien.The flame-retardant polymer molding composition particularly preferably contains from 5 to 30% by weight of diorganylphosphinic acid salts according to the invention or flame retardant composition according to the invention,
5 to 90% by weight of polymer or mixtures thereof
5 to 40% by weight of additives
5 to 40 wt .-% filler or reinforcing materials.

Bevorzugt handelt es sich bei den Polymeren um Polymere von Mono- und Diolefinen, beispielsweise Polypropylen, Polyisobutylen, Polybuten-1, Poly-4-methylpenten-1, Polyisopren oder Polybutadien sowie Polymerisate von Cycloolefinen; ferner Polyethylen (das gegebenenfalls vernetzt sein kann) sowie Mischungen davon.The polymers are preferably polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and also polymers of cycloolefins; also polyethylene (which may optionally be crosslinked) and mixtures thereof.

Bevorzugt handelt es sich bei den Polymeren um Copolymere von Mono- und Diolefinen untereinander oder mit anderen Vinylmonomeren, wie z. B. Ethylen-Propylen-Copolymere, ferner Mischungen solcher Copolymere untereinander, z. B. Polypropylen/Ethylen-Propylen-Copolymere, LDPE/Ethylen-Vinylacetat-Copolymere, LDPE/Ethylen-Acrylsäure-Copolymere, LLDPE/Ethylen-Vinylacetat-Copolymere, LLDPE/Ethylen-Acrylsäure-Copolymere und alternierend oder statistisch aufgebaute Polyalkylen/Kohlenstoffmonoxid-Copolymere und deren Mischungen mit anderen Polymeren wie z. B. Polyamiden.Preferably, the polymers are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as. For example, ethylene-propylene copolymers, mixtures of such copolymers with each other, for. Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or random polyalkylene / carbon monoxide copolymers. Copolymers and their blends with other polymers such. B. polyamides.

Bevorzugt handelt es sich bei den Polymeren um Kohlenwasserstoffharze (z. B. C5-C9) inklusive hydrierte Modifikationen davon (z. B. Klebrigmacherharze) und Mischungen von Polyalkylenen und Stärke.The polymers are preferably hydrocarbon resins (eg C 5 -C 9 ) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.

Bevorzugt handelt es sich bei den Polymeren um Polystyrol, Poly-(p-methylstyrol), Poly-(alpha-methylstyrol).
Bevorzugt handelt es sich bei den Polymeren um Copolymere von Styrol oder alpha-Methylstyrol mit Dienen oder Acrylderivaten, wie z. B. Styrol-Butadien, Styrol-Acrylnitril, Styrol-Alkylmethacrylat, Styrol-Butadien-Alkylacrylat und -methacrylat, Styrol-Maleinsäureanhydrid, Styrol-Acrylnitril-Methylacrylat; Mischungen von hoher Schlagzähigkeit aus Styrol-Copolymeren und einem anderen Polymer, wie z. B. einem Polyacrylat, einem Dien-Polymeren oder einem Ethylen-Propylen-Dien-Terpolymeren; sowie Blockcopolymere des Styrols, wie z. B. Styrol-Butadien-Styrol, Styrol-Isopren-Styrol, Styrol-Ethylen/Butylen-Styrol oder Styrol-Ethylen/Propylen-Styrol.The polymers are preferably polystyrene, poly (p-methylstyrene), poly (alpha-methylstyrene).
Preferably, the polymers are copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength of styrene copolymers and another polymer, such as. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

Bevorzugt handelt es sich bei den Polymeren um Pfropfcopolymere von Styrol oder alpha-Methylstyrol, wie z. B. Styrol auf Polybutadien, sowie deren Mischungen, wie sie z. B. als so genannte ABS-, MBS-, ASA- oder AES-Polymere bekannt sind.Preferably, the polymers are graft copolymers of styrene or alpha-methylstyrene, such as. As styrene on polybutadiene, and mixtures thereof, such as. B. as so-called ABS, MBS, ASA or AES polymers are known.

Bevorzugt handelt es sich bei den Polymeren um halogenhaltige Polymere, wie z. B. Polychloropren, Chlorkautschuk, chloriertes und bromiertes Copolymer aus Isobutylen-Isopren (Halobutylkautschuk), chloriertes oder chlorsulfoniertes Polyethylen, Copolymere von Ethylen und chloriertem Ethylen, Epichlorhydrinhomo- und -copolymere, insbesondere Polymere aus halogenhaltigen Vinylverbindungen, wie z. B. Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylfluorid, Polyvinylidenfluorid; sowie deren Copolymere, wie Vinylchlorid-Vinylidenchlorid, Vinylchlorid-Vinylacetat oder Vinylidenchlorid-Vinylacetat.Preferably, the polymers are halogen-containing polymers, such as. Polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogenated vinyl compounds, such as Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

Bevorzugt handelt es sich bei den Polymeren um Polymere, die sich von alpha-, beta-ungesättigten Säuren und deren Derivaten ableiten, wie Polyacrylate und Polymethacrylate und um Copolymere der genannten Monomeren untereinander oder mit anderen ungesättigten Monomeren, wie z. B. Acrylnitril-Butadien-Copolymere.The polymers are preferably polymers which are derived from alpha-, beta-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, and copolymers of said monomers with one another or with other unsaturated monomers, such as. For example, acrylonitrile-butadiene copolymers.

Bevorzugt handelt es sich bei den Polymeren um Polymere, die sich von ungesättigten Alkoholen und Aminen bzw. deren Acylderivaten oder Acetalen ableiten, wie Polyvinylalkohol, Polyvinylacetat, -stearat, -benzoat, -maleat, Polyvinylbutyral, Polyallylphthalat, Polyallylmelamin; sowie deren Copolymere mit Olefinen.The polymers are preferably polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins.

Bevorzugt handelt es sich bei den Polymeren um Homo- und Copolymere von cyclischen Ethern, wie Polyalkylenglykole, Polyethylenoxyd, Polypropylenoxyd oder deren Copolymere mit Bisglycidylethern.The polymers are preferably homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

Bevorzugt handelt es sich bei den Polymeren um Polyacetale, wie Polyoxymethylen, sowie solche Polyoxymethylene, die Comonomere, wie z. B. Ethylenoxid, enthalten; Polyacetale, die mit thermoplastischen Polyurethanen, Acrylaten oder MBS modifiziert sind.The polymers are preferably polyacetals, such as polyoxymethylene, as well as those polyoxymethylenes, the comonomers, such as. For example, ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

Bevorzugt handelt es sich bei den Polymeren um Polyphenylenoxide und -sulfide und deren Mischungen mit Styrolpolymeren oder Polyamiden.The polymers are preferably polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

Bevorzugt handelt es sich bei den Polymeren um Polyurethane, die sich von Polyethern, Polyestern und Polybutadienen mit endständigen Hydroxylgruppen einerseits und aliphatischen oder aromatischen Polyisocyanaten andererseits ableiten, sowie deren Vorprodukte.The polymers are preferably polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof.

Bevorzugt handelt es sich bei den Polymeren um Polyamide und Copolyamide, die sich von Diaminen und Dicarbonsäuren und/oder von Aminocarbonsäuren oder den entsprechenden Lactamen ableiten, wie Polyamid 2,12, Polyamid 4, Polyamid 4,6, Polyamid 6, Polyamid 6,6, Polyamid 6,9, Polyamid 6,10, Polyamid 6,12, Polyamid 6,66, Polyamid 7, Polyamid 7,7, Polyamid 8, Polyamid 8,8, Polyamid 9, Polyamid 9,9, Polyamid 10, Polyamid 10,9, Polyamid 10,10, Polyamid 11, Polyamid 12, aromatische Polyamide ausgehend von m-Xylol, Diamin und Adipinsäure; Polyamide, hergestellt aus Hexamethylendiamin und Iso- und/oder Terephthalsäure und gegebenenfalls einem Elastomer als Modifikator, z. B. Poly-2,4,4-trimethylhexamethylen-terephthalamid oder Poly-m-phenylenisophthalamid. Blockcopolymere der vorstehend genannten Polyamide mit Polyolefinen, Olefin-Copolymeren, lonomeren oder chemisch gebundenen oder gepfropften Elastomeren; oder mit Polyethern, wie z. B. mit Polyethylenglykol, Polypropylenglykol oder Polytetramethylenglykol. Ferner mit EPDM oder ABS modifizierte Polyamide oder Copolyamide; sowie während der Verarbeitung kondensierte Polyamide ("RIM-Polyamidsysteme").The polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2,12, polyamide 4, polyamide 4,6, polyamide 6, polyamide 6,6 , Polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6,66, polyamide 7, polyamide 7,7, polyamide 8, polyamide 8,8, polyamide 9, polyamide 9,9, polyamide 10, polyamide 10 , 9, polyamide 10, 10, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for. As poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").

Bevorzugt handelt es sich bei den Polymeren um Polyharnstoffe, Polyimide, Polyamidimide, Polyetherimide, Polyesterimide, Polyhydantoine und Polybenzimidazole.The polymers are preferably polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

Bevorzugt handelt es sich bei den Polymeren um Polyester, die sich von Dicarbonsäuren und Dialkoholen und/oder von Hydroxycarbonsäuren oder den entsprechenden Lactonen ableiten, wie Polyethylenterephthalat, Polybutylenterephthalat, Poly-1,4-dimethylolcyclohexanterephthalat, Polyhydroxybenzoate, sowie Block-Polyetherester, die sich von Polyethern mit Hydroxylendgruppen ableiten; ferner mit Polycarbonaten oder MBS modifizierte Polyester.The polymers are preferably polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates and also block polyether esters which differ from Derive hydroxyl-terminated polyethers; also with polycarbonates or MBS modified polyester.

Geeignete Polymeren sind auch Polycarbonate und Polyestercarbonate, Polysulfone, Polyethersulfone und Polyetherketone; vernetzte Polymere, die sich von Aldehyden einerseits und Phenolen, Harnstoff oder Melamin andererseits ableiten, wie Phenol-Formaldehyd-, Harnstoff-Formaldehyd- und Melamin-Formaldehydharze. Trocknende und nicht-trocknende Alkydharze.Suitable polymers include polycarbonates and polyestercarbonates, polysulfones, polyethersulfones and polyetherketones; crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins. Drying and non-drying alkyd resins.

Bevorzugt handelt es sich bei den Polymeren um ungesättigte Polyesterharze, die sich von Copolyestern gesättigter und ungesättigter Dicarbonsäuren mit mehrwertigen Alkoholen, sowie Vinylverbindungen als Vernetzungsmittel ableiten, wie auch deren halogenhaltige, schwerbrennbare Modifikationen.The polymers are preferably unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their halogen-containing, hardly combustible modifications.

Bevorzugt handelt es sich bei den Polymeren um vernetzbare Acrylharze, die sich von substituierten Acrylsäureestern ableiten, wie z. B. von Epoxyacrylaten, Urethanacrylaten oder Polyesteracrylaten.Preferably, the polymers are crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.

Bevorzugt handelt es sich bei den Polymeren um Alkydharze, Polyesterharze und Acrylatharze, die mit Melaminharzen, Harnstoffharzen, Isocyanaten, Isocyanuraten, Polyisocyanaten oder Epoxidharzen vernetzt sind.The polymers are preferably alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

Bevorzugt handelt es sich bei den Polymeren um vernetzte Epoxidharze, die sich von aliphatischen, cycloaliphatischen, heterocyclischen oder aromatischen Glycidylverbindungen ableiten, z. B. Produkte von Bisphenol-A-diglycidylethern, Bisphenol-F-diglycidylethern, die mittels üblichen Härtern wie z. B. Anhydriden oder Aminen mit oder ohne Beschleunigern vernetzt werden.Preferably, the polymers are crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. B. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, by conventional hardeners such. As anhydrides or amines can be crosslinked with or without accelerators.

Bevorzugt handelt es sich bei den Polymeren um Mischungen (Polyblends) der vorgenannten Polymeren, wie z. B. PP/EPDM, Polyamid/EPDM oder ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/Acrylate, POM/thermoplastisches PUR, PC/thermoplastisches PUR, POM/Acrylat, POM/MBS, PPO/HIPS, PPO/PA 6.6 und Copolymere, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS oder PBT/PET/PC.Preferably, the polymers are mixtures (polyblends) of the aforementioned polymers, such as. PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC ,

Bevorzugte Formen für Verstärkungsmaterialien für flammgeschützte Polymerformmassen und flammgeschützte Polymer-Formkörper sind Fasern, Vliese, Matten, Gewebe, Stränge, Bänder, Schläuche, Litzen, Massiv-, Form- und Hohlkörper.Preferred forms of reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer moldings are fibers, nonwovens, mats, fabrics, strands, tapes, hoses, strands, solid, molded and hollow bodies.

Bevorzugte Materialien für Verstärkungsmaterialien für flammgeschützte Polymerformmassen und flammgeschützte Polymer-Formkörper sind anorganische Materialien wie Quarz-Glas, Kohlenstoff, Mineralien, Metall (Stahl, Aluminium, Magnesium, Molybdän, Wolfram), Keramik (Metalloxide).Preferred materials for reinforcing materials for flame-retardant polymer molding compounds and flame-retardant polymer molded articles are inorganic Materials such as quartz glass, carbon, minerals, metal (steel, aluminum, magnesium, molybdenum, tungsten), ceramics (metal oxides).

Bevorzugte Materialien für Verstärkungsmaterialien für flammgeschützte Polymerformmassen und flammgeschützte Polymer-Formkörper sind Polykondensate wie z. B. Polyamid-6, Polyamid-6.6, Polyamid-11, aromatische Polyamide, Poly-p-phenylenterephthalamid, Polyethylenglycolterephthalat, Poly-1,4-dimethylencyclohexanterephthalat, Polycarbonat, Polyurethan-Elastomere.Preferred materials for reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer moldings are polycondensates such. As polyamide-6, polyamide-6.6, polyamide-11, aromatic polyamides, poly-p-phenylene terephthalamide, polyethylene glycol terephthalate, poly-1,4-dimethylencyclohexanterephthalat, polycarbonate, polyurethane elastomers.

Bevorzugte Materialien für Verstärkungsmaterialien für flammgeschützte Polymerformmassen und flammgeschützte Polymer-Formkörper sind Polymerisate wie z. B. Polyethylen, Polypropylen, Polyacrylnitril-Homopolymer, Polyacrylnitril-Mischpolymer, Modacryle, ataktisches Polyvinylchlorid, syndiotaktisches Polyvinylchlorid, Polyvinylalkohol, Polytetrafluorethylen, Polystyrol.Preferred materials for reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer moldings are polymers such. Polyethylene, polypropylene, polyacrylonitrile homopolymer, polyacrylonitrile copolymer, modacrylic, atactic polyvinyl chloride, syndiotactic polyvinyl chloride, polyvinyl alcohol, polytetrafluoroethylene, polystyrene.

Bevorzugte Materialien für Verstärkungsmaterialien für flammgeschützte Polymerformmassen und flammgeschützte Polymer-Formkörper sind natürliche und halbsynthetische Fasern (Viscosecellulose, Kupfercellulose, Celluloseacetat, Cellulosetriacetat, Flachs, Hanf, Sisal, Jute, Ramie, Baumwolle).Preferred materials for reinforcing materials for flame-retardant polymer molding compositions and flame-retardant polymer molded articles are natural and semisynthetic fibers (viscose cellulose, copper cellulose, cellulose acetate, cellulose triacetate, flax, hemp, sisal, jute, ramie, cotton).

Die Zugabe von Glasfasern zu Polyamiden innerhalb der erfindungsgemäßen Konzentrationsbereiche führt zu einer bedeutenden Steigerung bei Festigkeit, Steifheit, Erweichungstemperatur, Schleiffestigkeit und Formbeständigkeit.The addition of glass fibers to polyamides within the concentration ranges of the invention results in a significant increase in strength, stiffness, softening temperature, abrasion resistance, and dimensional stability.

Ein erfindungsgemäßes Verfahren zur Herstellung von flammgeschützten Polymerformmassen besteht darin die Flammschutzmittel-Zusammensetzungen und/oder Diorganylphosphinsäure-Salze mit dem Polymergranulat und evtl. Additiven in einem Mischer zu vermischen und in einem erfindungsgemäßen Compoundieraggregat unter erfindungsgemäßen Bedingungen in der Polymerschmelze zu homogenisieren. Der homogenisierte Formmassen-Strang wird abgezogen, im Wasserbad gekühlt und anschließend granuliert.An inventive method for the production of flame-retardant polymer molding compositions is to mix the flame retardant compositions and / or Diorganylphosphinsäure salts with the polymer granules and any additives in a mixer and homogenize in a compounding unit according to the invention under conditions according to the invention in the polymer melt. The homogenized molding material strand is drawn off, cooled in a water bath and then granulated.

In einer anderen Ausführungsform werden die Flammschutzmittel-Zusammensetzungen und/oder Diorganylphosphinsäure-Salze und/oder die Additive in einem Extruder durch einen Seiteneinzug zu dem Polymerstrom zudosiert und homogenisiert.In another embodiment, the flame retardant compositions and / or diorganylphosphinic acid salts and / or the additives metered in an extruder through a side feeder to the polymer stream and homogenized.

Die erfindungsgemäßen flammgeschützten Polymerformmasse haben eine Restfeuchte von 0,01 bis 10 Gew.-%, bevorzugt von 0,1 bis 1 Gew.-%. Restfeuchten oberhalb der erfindungsgemäß bevorzugten Bereiche bewirken einen verstärkten Polymerabbau.The flame-retardant polymer molding compositions of the invention have a residual moisture content of from 0.01 to 10% by weight, preferably from 0.1 to 1% by weight. Residual moistures above the inventively preferred ranges cause increased polymer degradation.

Erfindungsgemäß sind bei Polybutylenterephthalat-Formmassen SV-Zahlen von 750 bis 1.400 bevorzugt, 950 bis 1.300 besonders bevorzugt und 1.000 bis 1.200 besonders bevorzugt.According to the invention, in the case of polybutylene terephthalate molding compositions, SV numbers of 750 to 1,400 are preferred, 950 to 1,300 are particularly preferred, and 1,000 to 1,200 are particularly preferred.

Zur Beurteilung der Verträglichkeit kann auch der Volumenfließindex (Melt Flow Index, MFI, MVR) herangezogen werden. Ein starker Anstieg des MVR-Wertes deutet auf Polymerabbau hin.To assess the compatibility, the volume flow index (Melt Flow Index, MFI, MVR) can also be used. A strong increase in the MVR value indicates polymer degradation.

Bei erfindungsgemäßen glasfaserverstärkten flammgeschützten Polymerformmassen auf Basis von Polyamid 6.6 beträgt der Wert 2 bis 200 cm3/min (275 °C, 5 kg).In the case of glass fiber-reinforced flame-retardant polymer molding compositions based on polyamide 6.6 according to the invention, the value is from 2 to 200 cm 3 / min (275 ° C., 5 kg).

Die erfindungsgemäßen flammgeschützten Polymerformmassen eignen sich zur Herstellung von Fasern, Folien und Formkörpern, insbesondere für Anwendungen im Elektro- und Elektronikbereich.The flame-retardant polymer molding compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.

Erfindungsgemäß bevorzugt ist die Anwendung der erfindungsgemäßen flammgeschützten Polymerformkörpern als Lampenteile wie Lampenfassungen und -halterungen, Stecker und Steckerleisten, Spulenkörper, Gehäuse für Kondensatoren oder Schaltschütze sowie Sicherungsschalter, Relaisgehäuse und Reflektoren.Preferred according to the invention is the use of the flame-retardant polymer moldings according to the invention as lamp parts such as lampholders and holders, plugs and plug strips, bobbins, housings for capacitors or contactors, as well as fuse switches, relay housings and reflectors.

Bei dem Polymer der Polymerformkörper, -Filme, -Fäden und -Fasern handelt es sich bevorzugt um ein thermoplastisches oder duroplastisches Polymer.The polymer of the shaped polymer bodies, films, filaments and fibers is preferably a thermoplastic or thermosetting polymer.

Überraschend wurde gefunden, dass die mechanischen Eigenschaften von Polymerformkörpern, die auf den erfindungsgemäßen Diorganylphosphinsäure-Salzen, Flammschutzmitteln oder flammgeschützten Formmassen basieren, erheblich besser sind, als der Stand der Technik.Surprisingly, it has been found that the mechanical properties of polymer moldings based on the diorganylphosphinic acid salts according to the invention, Flame retardants or flame-retardant molding compounds are considerably better than the prior art.

Bevorzugt beträgt der E-Modul von Polymerformkörpern, die auf den erfindungsgemäßen Diorganylphosphinsäure-Salzen, Flammschutzmittein oder flammgeschützten Formmassen und Polybutylenterephthalat, Polyamid 6.6 oder Polyamid 6 basieren, 10.000 bis 12.000 N/mm2.The modulus of elasticity of polymer moldings based on the diorganylphosphinic acid salts according to the invention, flame retardant or flameproofed molding compositions and polybutylene terephthalate, polyamide 6.6 or polyamide 6 is preferably from 10,000 to 12,000 N / mm 2 .

Bevorzugtes Verfahren zur Herstellung von flammgeschützten Polymerformkörpern ist das Spritzgießen und Pressen, Schaumspritzgießen, Gasinnendruck-Spritzgießen, Blasformen, Foliengießen, Kalandern, Laminieren, Beschichten, Spinnen etc.Preferred method for the production of flame-retardant polymer moldings is injection molding and pressing, foam injection molding, gas injection molding, blow molding, film casting, calendering, laminating, coating, spinning, etc.

Bevorzugte Additive für flammgeschützte Polymerformmassen und flammgeschützte Polymer-Formkörper sind Antioxidantien, UV-Absorber und Lichtschutzmittel; Gleitmittel, Farbmittel, Antistatika Nukleierungsmittel; Füllstoffe usw.Preferred additives for flame-retardant polymer molding compositions and flame-retardant polymer moldings are antioxidants, UV absorbers and light stabilizers; Lubricants, colorants, antistatic agents, nucleating agents; Fillers etc.

Erfindungsgemäß ist eine Flammschutz-Beschichtung enthaltend mindestens 1 bis 50 % erfindungsgemäße Flammschutzmittel-Zusammensetzung 0 bis 60 % Ammoniumpolyphosphat.According to the invention, a flame retardant coating containing at least 1 to 50% of the inventive flame retardant composition is 0 to 60% ammonium polyphosphate.

ExperimentellesExperimental Bestimmung der Kornverteilung mit dem Microtrac GranulometerDetermination of grain distribution with the Microtrac Granulometer

Die Teilchengröße in wässriger Dispersion wird mit Hilfe eines Granulometer Microtrac ASVR/FRA der Fa. Leeds u. Northrup bestimmt. Gemessen wird die Reflexion bzw. Beugung eines Laserstrahls beim Durchdringen der Dispersion. Hierfür werden 400 ml Ethanol durch die Lasermesszelle gepumpt. Automatisch wird die Festkörperprobe (z. B. 70 mg) zudosiert und nach 10 min die Teilchengrößenverteilung bestimmt. Die Auswertungseinheit des Gerätes berechnet den d50- und den d90-Wert.The particle size in aqueous dispersion is determined using a granulometer Microtrac ASVR / FRA from Leeds et al. Northrup determined. The reflection or diffraction of a laser beam when penetrating the dispersion is measured. For this purpose, 400 ml of ethanol are pumped through the laser measuring cell. The solid sample (eg 70 mg) is added automatically and the particle size distribution is determined after 10 minutes. The evaluation unit of the device calculates the d50 and d90 values.

Bestimmung des Gesamt-Sulfat-GehaltesDetermination of the total sulphate content

Eine Probe des erfindungsgemäßen Diorganylphosphinsäure-Salzes wird in einem Lösungsmittel (bevorzugt Wasser, Natronlauge oder Salzsäure) gelöst und das Sulfat nach den üblichen Verfahren (bevorzugt ist die lonenchromatographie) quantifiziert.A sample of the diorganylphosphinic acid salt according to the invention is dissolved in a solvent (preferably water, sodium hydroxide or hydrochloric acid) and the Sulphate according to the usual methods (preferably, the ion chromatography) is quantified.

Bestimmung des löslichen Sulfat-GehaltesDetermination of the soluble sulphate content

90 g einer 2 %igen Isopropanol-Lösung werden einem 250 ml Becherglas eingewogen und in einem Temperierbad auf 90 °C erwärmt und mit einer Dissolverscheibe mit 900 U/min gerührt. Dann werden 10 g Diorganylphosphinsäure-Salz zugegeben. Die Suspension wird 5 min bei 900 U/min und bei 90 °C gerührt. Der Feststoff wird mit einer Nutsche (Filter: Schwarzband, 9 cm Durchmesser) abgenutscht und der Filterkuchen anschließend mit 20 g ca. 90 °C heißem VE-Wasser gewaschen. Das Filtrat wird auf 100 g mit VE-Wasser aufgefüllt. Die Lösung wird mittels lonenchromatographie auf den Sulfatgehalt analysiert. Der lösliche Sulfatgehalt berechnet sich wie folgt: Sulfatgehalt (Probe) [mg/kg] = Sulfatgehalt (im Filtrat) [mg/kg] * Endvolumen [mg] / Einwaage Diorganylphosphinsäure-Salz [mg]90 g of a 2% isopropanol solution are weighed into a 250 ml beaker and heated to 90 ° C. in a temperature-controlled bath and stirred with a dissolver disk at 900 rpm. Then 10 g of diorganylphosphinic acid salt are added. The suspension is stirred for 5 minutes at 900 rpm and at 90 ° C. The solid is filtered off with a suction filter (filter: black belt, 9 cm in diameter) and the filter cake is subsequently washed with 20 g of demineralized water at about 90 ° C. The filtrate is made up to 100 g with deionised water. The solution is analyzed by means of ion chromatography for the sulfate content. The soluble sulphate content is calculated as follows: sulphate content (sample) [mg / kg] = sulphate content (in the filtrate) [mg / kg] * final volume [mg] / initial weight diorganylphosphinic acid salt [mg]

Bestimmung der SV-Zahl (Spezifische Viskosität)Determination of the SV number (specific viscosity)

0,5 g der Polymerprobe (z. B. PBT) werden mit 50 ml Dichloressigsäure (LM) in einen 250 ml Erlenmeyerkolben mit Schliffstopfen eingewogen. Die Probe wird unter Rühren bei 25 °C über einen Zeitraum von 16h gelöst. Die Lösung wird über eine G1-Glasfritte filtriert. 20 ml der Lösung werden in die Kapillare gefüllt, in das (Ubbelohde)
Kapillarviskosimeter eingehängt und auf 25 °C temperiert. Der SV-Wert errechnet sich nach der Formel: SV-Wert=100*[Durchlaufzeit (Probenlösung)/Durchlaufzeit (LM)-1].0.5 g of the polymer sample (eg PBT) is weighed with 50 ml of dichloroacetic acid (LM) into a 250 ml Erlenmeyer flask with a ground stopper. The sample is dissolved with stirring at 25 ° C over a period of 16h. The solution is filtered through a G1 glass frit. 20 ml of the solution are filled into the capillary into which (Ubbelohde)
Capillary viscometer mounted and heated to 25 ° C. The SV value is calculated according to the formula: SV value = 100 * [cycle time (sample solution) / cycle time (LM) -1].

Statt Dichloressigsäure kann für Polyethylenterephthalat und Polybutylenterephtalat auch ein Gemisch von Phenol und 1,2-Dichlorbenzol (1:1, w/w) oder m-Kresol eingesetzt werden. Für Polyamid können Schwefelsäure, Ameisensäure oder m-Kresol verwendet werden.Instead of dichloroacetic acid, a mixture of phenol and 1,2-dichlorobenzene (1: 1, w / w) or m-cresol can also be used for polyethylene terephthalate and polybutylene terephthalate. For polyamide sulfuric acid, formic acid or m-cresol can be used.

Herstellung, Verarbeitung und Prüfung von flammhemmenden Compounds und Kunststoff-FormkörperProduction, processing and testing of flame retardant compounds and plastic moldings

Die Flammschutzkomponenten werden mit dem Polymergranulat und evtl. Additiven vermischt und auf einem Doppelschnecken-Extruder (Typ Leistritz LSM 30/34) bei Temperaturen von 230 bis 260 °C (glasfaserverstärktes PBT) bzw. von 260 bis 280 °C (glasfaserverstärktes PA 66) eingearbeitet. Der homogenisierte Polymerstrang wurde abgezogen, im Wasserbad gekühlt und anschließend granuliert.The flame retardant components are mixed with the polymer granules and any additives and on a twin-screw extruder (type Leistritz LSM 30/34) at temperatures of 230 to 260 ° C (glass fiber reinforced PBT) or from 260 to 280 ° C (glass fiber reinforced PA 66) incorporated. The homogenized polymer strand was stripped off, cooled in a water bath and then granulated.

Nach ausreichender Trocknung wurden die Formmassen auf einer Spritzgießmaschine (Typ Aarburg Allrounder) bei Massetemperaturen von 240 bis 270 °C (glasfaserverstärktes PBT) bzw. von 260 bis 290 °C (glasfaserverstärktes PA 66) zu Prüfkörpern verarbeitet.After sufficient drying, the molding compositions were processed on an injection molding machine (Aarburg Allrounder type) at melt temperatures of 240 to 270 ° C. (glass-fiber-reinforced PBT) or from 260 to 290 ° C. (glass-fiber-reinforced PA 66) to test specimens.

Beispiel 1 (Vergleich, unbehandeltes Polymer)Example 1 (comparison, untreated polymer)

In einem Laborkneter werden 70 g vorgetrocknetes Celanex® 2500 (PBT) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 1386 bestimmt.In a laboratory kneader, 70 g of predried Celanex ® 2500 (PBT) are mixed at 240 ° C over a period of 6 minutes at 40 rpm. After cooling, a sample of the mass determines the SV value to be 1386.

Beispiel 2, VergleichExample 2, comparison

In einem Laborkneter werden 56 g vorgetrocknetes Celanex® 2500 (PBT) und 14 g Diorganylphosphinsäure-Salz nach DE19851618 (1997 DE128), Beispiel 2 (Acetatgehalt 8.800 ppm) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 578 bestimmt. Dieser Wert zeigt unzureichende Verträglichkeit des Diorganylphosphinsäure-Salzes mit dem Polymer an.In a laboratory kneader, 56 g of predried Celanex ® 2500 (PBT) and 14 g of diorganylphosphinic salt by DE19851618 (1997 DE128), Example 2 (acetate content 8,800 ppm) at 240 ° C for a period of 6 min at 40 rpm mixed. After cooling, a sample of the mass determines the SV value to be 578. This value indicates inadequate compatibility of the diorganylphosphinic acid salt with the polymer.

Beispiel 3, VergleichExample 3, comparison

In einem Laborkneter werden 56 g vorgetrocknetes Celanex® 2500 (PBT) und 14 g Diorganylphosphinsäure-Salz nach DE-19 851 618 (1997 DE128), Beispiel 4 (Acetatgehalt 4.500 ppm) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 589 bestimmt. Dieser Wert zeigt unzureichende Verträglichkeit des Diorganylphosphinsäure-Salzes mit dem Polymer an.In a laboratory kneader, 56 g of predried Celanex ® 2500 (PBT) and 14 g of diorganylphosphinic salt by DE-19 851 618 (1997 DE128), Example 4 (acetate content 4500 ppm) at 240 ° C over a period of 6 min at 40 rpm mixed. After cooling, a sample of the mass determines the SV value to be 589. This value indicates inadequate compatibility of the diorganylphosphinic acid salt with the polymer.

Beispiel 4Example 4

In einem Laborkneter werden 56 g vorgetrocknetes Celanex® 2500 (PBT) und 14 g Diorganylphosphinsäure-Salz (Gesamt-Acetatgehalt 3.000 ppm, löslicher AcetatGehalt 1.680 ppm) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 673 bestimmt.In a laboratory kneader, 56 g of predried Celanex ® 2500 (PBT) and 14 g of diorganylphosphinic salt (total acetate 1,680 ppm 3,000 ppm, soluble acetate content) were mixed at 240 ° C over a period of 6 minutes at 40 rpm. After cooling, a sample of the mass determines the SV value to be 673.

Beispiel 5, VergleichExample 5, Comparison

In einem Laborkneter werden 56 g vorgetrocknetes Celanex® 2500 (PBT) und 14 g Diorganylphosphinsäure-Salz (Gesamt-Sulfatgehalt 5.070 ppm, löslicher Sulfat-Gehalt 1.300 ppm) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 582 bestimmt (unreichende Verträglichkeit des Diorganylphosphinsäure-Salzes mit dem Polymer).In a laboratory kneader, 56 g of predried Celanex ® 2500 (PBT) and 14 g of diorganylphosphinic salt (total sulfate content of 1,300 ppm 5,070 ppm of soluble sulfate content) were mixed at 240 ° C over a period of 6 minutes at 40 rpm. After cooling, a sample of the mass determines the SV value to be 582 (unsatisfactory compatibility of the diorganylphosphinic acid salt with the polymer).

Beispiel 6Example 6

In einem Laborkneter werden 56 g vorgetrocknetes Celanex® 2500 (PBT) und 14 g Diorganylphosphinsäure-Salz (Gesamt-Sulfatgehalt 2.510 ppm, löslicher Sulfat-Gehalt 42 ppm) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 1012 bestimmt.In a laboratory kneader, 56 g of predried Celanex ® 2500 (PBT) and 14 g Diorganylphosphinic salt (total sulfate content of 42 ppm 2,510 ppm of soluble sulfate content) were mixed at 240 ° C over a period of 6 minutes at 40 rpm. After cooling, a sample of the mass determines the SV value to be 1012.

Beispiel 7Example 7

In einem Laborkneter werden 56 g vorgetrocknetes Celanex® 2500 (PBT) und 14 g Diorganylphosphinsäure-Salz (Gesamt-Sulfatgehalt 640 ppm, löslicher Sulfat-Gehalt 521 ppm) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 1158 bestimmt.In a laboratory kneader, 56 g of predried Celanex ® 2500 (PBT) and 14 g of diorganylphosphinic salt (total sulfate content of 521 ppm 640 ppm of soluble sulfate content) were mixed at 240 ° C over a period of 6 minutes at 40 rpm. After cooling, a sample of the mass determines the SV value to be 1158.

Beispiel 8Example 8

In einem Laborkneter werden 56 g vorgetrocknetes Celanex® 2500 (PBT) und 14 g Diorganylphosphinsäure-Salz (Gesamt-Sulfatgehalt 200 ppm, löslicher Sulfat-Gehalt 21 ppm) bei 240 °C über einen Zeitraum von 6 min bei 40 Upm gemischt. Nach dem Erkalten wird von einer Probe der Masse der SV-Wert zu 1196 bestimmt.In a laboratory kneader, 56 g of predried Celanex ® 2500 (PBT) and 14 g of diorganylphosphinic salt (total sulfate content of 200 ppm of soluble sulfate content 21 ppm) at 240 ° C over a period of 6 min at 40 rpm. After cooling, a sample of the mass determines the SV value to be 1196.

Beispiel 9, VergleichExample 9, comparison

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polybutylenterephthalat, 15 Gew.-% Phosphinsäuresalz aus Beispiel 2, 5 Gew.-% Melamincyanurat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 9.150 N/mm2 gemessen.According to the general procedure, a mixture of 50% by weight of polybutylene terephthalate, 15% by weight of phosphinic acid salt from Example 2, 5% by weight of melamine cyanurate and 30% by weight of glass fibers is added at 230 to 260 ° C. on a twin-screw extruder a polymer molding compound compounded. After drying, the molding compositions are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and an E modulus of 9,150 N / mm 2 measured.

Beispiel 10, VergleichExample 10, Comparison

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polybutylenterephthalat, 15 Gew.-% Phosphinsäuresalz aus Beispiel 3, 5 Gew.-% Melamincyanurat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 9.573 N/mm2 gemessen.According to the general procedure, a mixture of 50% by weight of polybutylene terephthalate, 15% by weight of phosphinic acid salt from Example 3, 5% by weight of melamine cyanurate and 30% by weight of glass fibers is added at 230 to 260 ° C. on a twin-screw extruder a polymer molding compound compounded. After drying, the molding compositions are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 9,573 N / mm 2 measured.

Beispiel 11Example 11

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polybutylenterephthalat, 13,3 Gew.-% Phosphinsäuresalz aus Beispiel 7, 6,7 Gew.-% Melamincyanurat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 10.350 N/mm2 gemessen. Weiterhin wurde eine UL-94 Klassifizierung von V-0 bestimmt. Wegen der günstigeren UL-94 Klassifizierung sind die Zusammensetzung der diesem Beispiel zugrunde liegenden Flammschutzformulierung enthaltend Phosphinsäuresalz und Melamincyanurat, die Zusammensetzung der diesem Beispiel zugrunde liegenden Polymerformmasse enthaltend Polybutylenterephthalat und Flammschutzformulierung (enthaltend Phosphinsäuresalz und Melamincyanurat) sowie die diesem Beispiel zugrunde liegende Polymerformkörper-Zusammensetzung enthaltend Polymerformmasse und Additive bevorzugt gegenüber solchen, die V-1 und V-2 Klassifizierungen ergeben.According to the general procedure, a mixture of 50% by weight of polybutylene terephthalate, 13.3% by weight of the phosphinic acid salt from Example 7, 6.7% by weight of melamine cyanurate and 30% by weight of glass fibers is heated on a twin-screw extruder at 230 to 260 ° C compounded to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 10,350 N / mm 2 measured. Furthermore, a UL-94 classification of V-0 was determined. Because of the more favorable UL-94 classification, the composition of the flame retardant formulation comprising phosphinic acid salt and melamine cyanurate on which this example is based is based on the composition of the polymer molding composition based on polybutylene terephthalate and flame retardant formulation (containing phosphinic acid salt and melamine cyanurate) and this example lying polymer molding composition containing polymer molding composition and additives over those which give V-1 and V-2 classifications.

Beispiel 12Example 12

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polybutylenterephthalat, 15 Gew.-% Phosphinsäuresalz aus Beispiel 8, 5 Gew.-% Melamincyanurat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 10.510 N/mm2 gemessen. Außerdem wird eine UL-94 Klassifizierung von V-0 bestimmt.According to the general procedure, a mixture of 50% by weight of polybutylene terephthalate, 15% by weight of phosphinic acid salt from Example 8, 5% by weight of melamine cyanurate and 30% by weight of glass fibers is added at 230 to 260 ° C. on a twin-screw extruder a polymer molding compound compounded. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 10,510 N / mm 2 measured. In addition, a UL-94 classification of V-0 is determined.

Beispiel 13Example 13

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polybutylenterephthalat, 13,3 Gew.-% Phosphinsäuresalz aus Beispiel 7, 6,7 Gew.-% Melaminpolyphosphat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und eine UL-94 Klassifizierung von V-0 bestimmt.According to the general procedure, a mixture of 50% by weight of polybutylene terephthalate, 13.3% by weight of the phosphinic acid salt from Example 7, 6.7% by weight of melamine polyphosphate and 30% by weight of glass fibers is heated on a twin-screw extruder at 230 to 260 ° C compounded to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and a UL-94 classification of V-0 determined.

Beispiel 14, VergleichExample 14, Comparison

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polyamid 6.6, 13,3 Gew.-% Phosphinsäuresalz aus Beispiel 2, 6,7 Gew.-% Melaminpolyphosphat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 9.000 N/mm2 gemessen. Außerdem wurde eine UL-94 Klassifizierung von V-0 bestimmt.According to the general procedure, a mixture of 50% by weight of polyamide 6.6, 13.3% by weight of phosphinic acid salt from example 2, 6.7% by weight of melamine polyphosphate and 30% by weight of glass fibers is heated to 230 on a twin-screw extruder compounded to 260 ° C to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and measured an E-modulus of 9,000 N / mm 2 . In addition, a UL-94 classification of V-0 was determined.

Beispiel 15Example 15

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polyamid 6.6, 13,3 Gew.-% Phosphinsäuresalz aus Beispiel 8, 6,7 Gew.-% Melaminpolyphosphat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 11.500 N/mm2 gemessen. Außerdem wurde eine UL-94 Klassifizierung von V-0 bestimmt. Wegen der günstigeren UL-94 Klassifizierung sind die Zusammensetzung der diesem Beispiel zugrunde liegenden Flammschutzformulierung enthaltend Phosphinsäuresalz und Melaminpolyphosphat, die Zusammensetzung der diesem Beispiel zugrunde liegenden Polymerformmasse enthaltend Polyamid und Flammschutzformulierung (enthaltend Phosphinsäuresalz und Melaminpolyphosphat) sowie die diesem Beispiel zugrunde liegende Polymerformkörper-Zusammensetzung enthaltend Polymerformmasse und Additive bevorzugt gegenüber solchen, die V-1 und V-2 Klassifizierungen ergeben.According to the general procedure, a mixture of 50% by weight of polyamide 6.6, 13.3% by weight of phosphinic acid salt from Example 8, 6.7% by weight of melamine polyphosphate and 30% by weight of glass fibers is heated to 230 on a twin-screw extruder up to 260 ° C compounded to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and an E-modulus of 11,500 N / mm 2 measured. In addition, a UL-94 classification of V-0 was determined. Because of the more favorable UL-94 classification, the composition of this example based flame retardant formulation containing phosphinic acid salt and melamine polyphosphate, the composition of this example underlying polymer molding composition containing polyamide and flame retardant formulation (containing phosphinic acid salt and melamine polyphosphate) and the example of this underlying polymer molding composition containing polymer molding composition and additives over those giving V-1 and V-2 classifications.

Beispiel 16, VergleichExample 16, Comparison

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polyamid 6.6, 15 Gew.-% Phosphinsäuresalz aus Beispiel 2, 4 Gew.-% Melaminpolyphosphat, 1 Gew.-% Zinkborat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 9.100 N/mm2 gemessen. Dieser E-Modul von einem Polymerformkörper auf Basis eines Phosphinsäuresalzes nach dem Stand der Technik ist schlechter als die der Beispiele 46 und 47, bei denen erfindungsgemäße Phosphinsäuresalze verwendet wurden.According to the general procedure, a mixture of 50% by weight of polyamide 6.6, 15% by weight of phosphinic acid salt from example 2, 4% by weight of melamine polyphosphate, 1% by weight of zinc borate and 30% by weight of glass fibers on a twin screw Extruder compounded at 230 to 260 ° C to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to form polymer molding and an E modulus of 9,100 N / mm 2 measured. This modulus of elasticity of a prior art phosphinic acid-based polymer molded product is inferior to that of Examples 46 and 47 in which phosphinic acid salts of the present invention were used.

Beispiel 17, VergleichExample 17, Comparison

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polyamid 6.6, 15 Gew.-% Phosphinsäuresalz aus Beispiel 3, 4 Gew.-% Melaminpolyphosphat, 1 Gew.-% Zinkborat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 9500 N/mm2 gemessen. Dieser E-Modul von einem Polymerformkörper auf Basis eines Phosphinsäuresalzes nach dem Stand der Technik ist schlechter als die der Beispiele 46 und 47, bei denen erfindungsgemäße Phosphinsäuresalze verwendet wurden.According to the general procedure, a mixture of 50% by weight of polyamide 6.6, 15% by weight of phosphinic acid salt from Example 3, 4% by weight of melamine polyphosphate, 1% by weight of zinc borate and 30% by weight of glass fibers on a twin-screw extruder is used. Extruder compounded at 230 to 260 ° C to a polymer molding composition. After drying, the molding compositions are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and an E modulus of 9500 N / mm 2 measured. This modulus of elasticity of a prior art phosphinic acid-based polymer molded product is inferior to that of Examples 46 and 47 in which phosphinic acid salts of the present invention were used.

Beispiel 18Example 18

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polyamid 6.6, 15 Gew.-% Phosphinsäuresalz aus Beispiel 8, 4 Gew.-% Melaminpolyphosphat, 1 Gew.-% Zinkborat und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 11.800 N/mm2 gemessen. Außerdem wird eine UL-94 Klassifizierung von V-0 bestimmt.According to the general procedure, a mixture of 50% by weight of polyamide 6.6, 15% by weight of phosphinic acid salt from Example 8, 4% by weight of melamine polyphosphate, 1% by weight of zinc borate and 30% by weight of glass fibers on a twin screw Extruder compounded at 230 to 260 ° C to a polymer molding composition. After drying, the molding compositions are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 11,800 N / mm 2 measured. In addition, a UL-94 classification of V-0 is determined.

Beispiel 19Example 19

Gemäß der allgemeinen Vorschrift wird eine Mischung von 50 Gew.-% Polyamid 6.6, 12,7 Gew.-% Phosphinsäuresalz aus Beispiel 7, 6,3 Gew.-% Melaminpolyphosphat, 1 Gew.-% Zinkoxid und 30 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und ein E-Modul von 10.100 N/mm2 gemessen. Außerdem wird eine UL-94 Klassifizierung von V-0 bestimmt.According to the general procedure, a mixture of 50 wt .-% polyamide 6.6, 12.7 wt .-% phosphinic acid salt from Example 7, 6.3 wt .-% melamine polyphosphate, 1 wt .-% zinc oxide and 30 wt .-% glass fibers compounded on a twin-screw extruder at 230 to 260 ° C to a polymer molding composition. After drying, the molding compositions are processed on an injection molding machine at 240 to 270 ° C to give polymer molding and an E-modulus of 10,100 N / mm 2 measured. In addition, a UL-94 classification of V-0 is determined.

Beispiel 20Example 20

Gemäß der allgemeinen Vorschrift wird eine Mischung von 58 Gew.-% Polyamid 6, 11,3 Gew.-% Phosphinsäuresalz aus Beispiel 8, 5,7 Gew.-% Melaminpolyphosphat und 25 Gew.-% Glasfasern auf einem Doppelschnecken-Extruder bei 230 bis 260 °C zu einer Polymerformmasse compoundiert. Nach Trocknung werden die Formmassen auf einer Spritzgießmaschine bei 240 bis 270 °C zu Polymerformkörper verarbeitet und eine UL-94 Klassifizierung von V-0 bestimmt.According to the general procedure, a mixture of 58% by weight of polyamide 6, 11.3% by weight of phosphinic acid salt from Example 8, 5.7% by weight of melamine polyphosphate and 25% by weight of glass fibers is heated to 230 on a twin-screw extruder compounded to 260 ° C to a polymer molding composition. After drying, the molding materials are processed on an injection molding machine at 240 to 270 ° C to form polymer bodies and a UL-94 classification of V-0 determined.

Verwendete ChemikalienUsed chemicals

Polybutylenterephthalat:polybutylene terephthalate: Celanex 2500, Fa. TiconaCelanex 2500, Ticona Polyamid 6.6:Polyamide 6.6: Ultramid A3, Fa. BASFUltramid A3, Fa. BASF Polyamid 6:Polyamide 6: Zytel 7301, Fa. Du PontZytel 7301, Du Pont Melaminpolyphosphat:melamine: Melapur 200/70, Fa. Ciba DSM-MelapurMelapur 200/70, Ciba DSM-Melapur Melamincyanurat:melamine: Melapur MC, Fa. Ciba DSM-MelapurMelapur MC, Ciba DSM-Melapur Zinkborat:Zinc borate: Firebrake 500, Fa. BoraxFirebrake 500, Fa. Borax Zinkoxid:Zinc oxide: Fa. RheinchemieFa. Rheinchemie Zinkhydroxystannat:hydroxystannate: Flamtard H, Fa. BlytheFlamtard H, Blythe Zinkstearat:Zinc stearate: Liga 101, Fa. Greven Fett-ChemieLeague 101, Fa. Greven Fett-Chemie Glasfasern 1:Glass fibers 1: Vetrotex EC 10 983, Fa. Saint-GobainVetrotex EC 10 983, Fa. Saint-Gobain Glasfasern 2:Glass fibers 2: PPG 3540, Fa. PPG Industries, IncPPG 3540, PPG Industries, Inc Tabelle 1Table 1 Beispielexample Acetatacetate Sulfatsulfate SV-ZahlSV index Gesamt [ppm]Total [ppm] Löslich [ppm]Soluble [ppm] Gesamt [ppm]Total [ppm] Löslich [ppm]Soluble [ppm] 1 (Vgl. Polymer)1 (see polymer) -- -- -- -- 13861386 2 (Vgl.) DE19851618, Bsp. 22 (Cf.) DE19851618, Ex. 2 88008800 -- -- -- 578578 3 (Vgl.) DE19851618, Bsp. 43 (Cf.) DE19851618, Ex. 4 45004500 -- -- -- 589589 5 (Vgl.)5 (Cf.) -- -- 50705070 13001300 582582 66 -- -- 25102510 4242 10121012 77 -- -- 640640 521521 11581158 88th -- -- 200200 2121 11961196 Tabelle 2Table 2 Beispielexample 9 (Vgl.)9 (Cf.) 10 (Vgl.)10 (Cf.) 1111 1212 1313 14 (Vgl.)14 (Cf.) 1515 16 (Vgl.)16 (Cf.) 17 (Vgl.)17 (Cf.) 1818 1919 2020 Polybutylenterephthalatpolybutylene terephthalate [Gew.-%][Wt .-%] 5050 5050 5050 5050 5050 -- -- -- -- -- -- -- Polyamid 6.6Polyamide 6.6 [Gew.-%][Wt .-%] -- -- -- -- -- 5050 5050 5050 5050 5050 5050 -- Polyamid 6Polyamide 6 [Gew.-%][Wt .-%] -- -- -- -- -- -- -- -- -- -- -- 5858 Phosphinsäuresalz Bsp. 2 (Vgl.)Phosphinic acid salt Ex. 2 (cf.) [Gew.-%][Wt .-%] 1515 -- -- -- -- 13,313.3 -- 1515 -- -- -- -- Phosphinsäuresalz Bsp. 3 (Vgl.)Phosphinic acid salt Ex. 3 (cf.) [Gew.-%][Wt .-%] -- 1515 -- -- -- -- -- -- 1515 -- -- -- Phosphinsäuresalz Bsp. 7Phosphinic acid salt Ex. 7 [Gew.-%][Wt .-%] -- -- 13,313.3 -- -- -- -- -- -- -- -- -- Phosphinsäuresalz Bsp. 8Phosphinic acid salt Ex. 8 [Gew.-%][Wt .-%] -- -- -- 1515 -- -- 13,313.3 -- -- -- -- 11,311.3 Phosphinsäuresalz Bsp. 7Phosphinic acid salt Ex. 7 [Gew.-%][Wt .-%] -- -- -- -- 13,313.3 -- -- -- -- -- 12,712.7 -- Phosphinsäuresalz Bsp. 6Phosphinic acid salt Ex. 6 [Gew.-%][Wt .-%] -- -- -- -- -- -- -- -- -- 1515 -- -- Melaminpolyphosphatmelamine [Gew.-%][Wt .-%] -- -- -- -- 6,76.7 6,76.7 6,76.7 22 44 44 6,36.3 5,75.7 Melamincyanuratmelamine [Gew.-%][Wt .-%] 55 55 6,76.7 55 -- -- -- -- -- -- -- -- Zinkboratzinc borate [Gew.-%][Wt .-%] -- -- -- -- -- -- -- 11 11 11 -- -- Zinkoxidzinc oxide [Gew.-%][Wt .-%] -- -- -- -- -- -- -- -- -- -- 11 -- Zinkhydroxystannathydroxystannate [Gew.-%][Wt .-%] -- -- -- -- -- -- -- -- -- -- -- -- Zinkstearatzinc stearate [Gew.-%][Wt .-%] -- -- -- -- -- -- -- -- -- -- -- -- Glasfasern 1Glass fibers 1 [Gew.-%][Wt .-%] 3030 3030 3030 3030 3030 -- -- -- -- -- -- -- Glasfasern 2Glass fibers 2 [Gew.-%][Wt .-%] -- -- -- -- -- 3030 3030 3030 3030 3030 3030 2525 E-ModulModulus [N/mm2][N / mm 2 ] 91509150 95739573 103501103501 105101105101 -- 90009000 1150011500 91009100 95009500 1180011800 1010010100 -- UL-94 KlassifizierungUL-94 classification -- V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0

Claims (16)

  1. A diorganylphosphinic salt of the formula (I)
    Figure imgb0006
     where
    R1 and R2 are identical or different and are C1-C6-alkyl, linear or branched, and/or aryl;
    M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, and/or a protonated nitrogen base;
    m is from 1 to 4 and
    x is from 1 to 4,
    wherein the total content of partially water-soluble, ionizable compounds and the water-soluble content of the partially water-soluble, ionizable compounds is from 8200 to 100 ppm and wherein the partially water-soluble, ionizable compounds comprise compounds which derive from acetates, from chlorides, from nitrates, from sulfates, from phosphites, or from phosphates, and wherein the total content of sulfate (partially water-soluble, ionizable compound) is from 3800 to 100 ppm, and the content of water-soluble sulfate (water-soluble content of the partially water-soluble, ionizable compound) is from 1200 to 10 ppm.
  2. The diorganylphosphinic salt of the formula (I) as claimed in claim 1, wherein M is aluminum, calcium, titanium, zinc, tin or zirconium.
  3. The diorganylphosphinic salt of the formula (I) as claimed in claim 1, wherein R1 and R2, identical or different, are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and/or phenyl.
  4. The diorganylphosphinic salt of the formula (I) as claimed in one or more of claims 1 to 3, wherein the diorganylphosphinic salts of the formula (I) comprise those from the group of aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate and any desired mixture thereof.
  5. The diorganylphosphinic salt of the formula (I) as claimed in one or more of claims 1 to 4, whose residual moisture level is from 0.01 to 10% by weight, whose particle size is from 0.1 to 1000 µm and whose bulk density is from 80 to 800 g/l.
  6. A process for preparation of diorganylphosphinic salts of the formula (I) as claimed in one or more of claims 1 to 5, which comprises reacting the diorganylphosphinic acid
    a) with a free base, or
    b) with the elemental metal of the desired cation, or
    c) in its alkali metal salt form, with a salt of the desired cation, or
    d) in the form of a reactive derivative, with a derivative of the desired cation for from 0.01 to 1 hours at from 0 to 300°C.
  7. The process as claimed in claim 6, wherein the free base comprises nitrogen bases, such as ammonia, amines, melamine, urea, biuret, guanidine, alkylguanidine, arylguanidine, diphenylguanidine, biguanide, biuret, allantoin, acetoguanamine, benzoguanamine, tolyltriazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, ethylenedimelamine, acetyleneurea, hydantoin, malonamide amidine, dimethylurea, 5,5-diphenylhydantoin, N,N'-diphenylurea, ethylenebis-5-triazone, glycine anhydride, tetramethylurea, triethanolamine and/or condensates of melamine.
  8. The process as claimed in claim 6, wherein the free base comprises an oxide, mixed metal oxide hydroxide, hydroxide, carbonate, hydroxide carbonate, or hydrogencarbonate of the desired cation.
  9. The process as claimed in one or more of claims 6 to 8, wherein the desired cations are Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, and/or K.
  10. The process as claimed in one or more of claims 6 to 9, wherein the salt of the desired cation comprises fluorides, chlorides, bromides, iodides, hypohalites, halites, halates, iodate, perhalates, perchlorate, oxides, hydroxides, peroxides, superoxides, sulfates, hydrogensulfates, sulfate hydrates, sulfites, peroxosulfates, nitrides, phosphides, nitrate, nitrate hydrates, nitrites, phosphates, peroxophosphates, phosphites, hypophosphites, pyrophosphates, carbonates, hydrogencarbonates, hydroxide carbonates, carbonate hydrates, silicates, hexafluorosilicates, hexafluorosilicate hydrates, stannates, borates, polyborates, peroxoborates, thiocyanates, cyanates, cyanides, chromates, chromites, molybdates, permanganate.
  11. The process as claimed in one or more of claims 6 to 9, wherein the salt of the desired cation compounds having organic anions from the group of the mono-, di-, oligo-, or polycarboxylic acids, and preferably the salt of the desired cation moreover comprises compounds having organic anions from the group of the mono-, di-, oligo-, or polycarboxylic acids such as formates, acetates, acetate hydrates, trifluoroacetate hydrates, propionates, butyrates, valerates, caprylates, oleates, stearates, oxalates, tartrates, citrates, citrate hydrates, benzoates, salicylates, lactate, lactate hydrates, acrylic acid, maleic acid, succinic acid, of amino acids (glycine), of acidic hydroxy functions (phenolates etc.), para-phenolsulfonates, para-phenolsulfonate hydrates, acetylacetonate hydrates, tannates, dimethyldithiocarbamates, trifluoromethanesulfonate, alkylsulfonates and/or aralkylsulfonates.
  12. The process as claimed in one or more of claims 6 to 11, wherein the reactive derivatives comprise diorganylphosphinic esters, diorganylphosphinic pyroesters and/or diorganylphosphinic chlorides.
  13. The use of diorganylphosphinic salts as claimed in one or more of claims 1 to 5 as flame retardants or in flame retardant compositions, where the flame retardant composition comprises from 50 to 99.9% by weight of a diorganylphosphinic salt as claimed in one or more of claims 1 to 5 and from 0.1 to 50% by weight of at least one additive, and where the additives derive from the group of melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetrakismelamine triphosphate, hexakismelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, melon polyphosphate, or from the group of oligomeric esters of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, guanidine; or from the group of the zinc compounds, such as zinc oxide, zinc hydroxide, zinc oxide hydrate, zinc carbonate, zinc stannate, zinc hydroxystannate, zinc silicate, zinc phosphate, zinc borate, zinc molybdate; or from the group of the carbodiimides and/or (poly)isocyanates, e.g. carbonylbiscaprolactam and/or styrene-acrylic polymers.
  14. The use of diorganylphosphinic salts as claimed in one or more of claims 1 to 5 in or for preparation of flame-retardant polymer molding compositions, or flame-retardant polymer moldings, flame-retardant polymer films, flame-retardant polymer filaments, or flame-retardant polymer fibers.
  15. The use as claimed in claim 13 or 14, wherein the polymers derive from the group of the thermoplastic polymers, such as polyester, polystyrene, or polyamide, and/or of the thermoset polymers.
  16. The use as claimed in claim 13, wherein the flame-retardant polymer molding compositions or polymer moldings, flame-retardant polymer films, flame-retardant polymer filaments, or flame-retardant polymer fibers comprise from 1 to 50% by weight of diorganylphosphinic salts as claimed in one or more of claims 1 to 17, from 1 to 99% by weight of polymer or of a mixture of these, from 0 to 60% by weight of additives, and from 0 to 60% by weight of filler or of reinforcing materials.
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